CN102499259A - Clothing degerming liquid and preparation method thereof - Google Patents
Clothing degerming liquid and preparation method thereof Download PDFInfo
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- CN102499259A CN102499259A CN201110369026XA CN201110369026A CN102499259A CN 102499259 A CN102499259 A CN 102499259A CN 201110369026X A CN201110369026X A CN 201110369026XA CN 201110369026 A CN201110369026 A CN 201110369026A CN 102499259 A CN102499259 A CN 102499259A
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Abstract
The invention relates to clothing degerming liquid and a preparation method thereof. The method comprises the following steps of: preparing mesoporous silicate nano-silver-loaded antibacterial agent suspension; preparing microemulsion containing an organic antibacterial agent; and adding and mixing an emulsifier, a chelating and anchoring stabilizer, a softener and a thickener. The clothing degerming liquid disclosed by the invention has high using safety, clothing degerming rate of over 99 percent and high stability. Due to the adoption of the clothing degerming liquid, after clothes are washed by water for 20 times, the antibacterial ratio of the clothes is still over 90 percent. The clothing degerming liquid has excellent antibacterial and durable performances, is non-toxic, has no irritation on the skin and has a deodorization effect on fabrics. The clothing degerming liquid disclosed by the invention has simple production process and low equipment investment, is easy for industrial production, is environmental-friendly and has strong market competitiveness.
Description
[technical field]
The invention belongs to the sterilization sterilization technology field.More specifically, the present invention relates to a kind of clothing bacteria-removing liquid, also relate to the preparation method of said clothing bacteria-removing liquid.
[background technology]
Washing machine is widely used in daily life, has brought convenience with quick for people's life.Use in washing machine in daily life bottom long afterwards often has one mouldy smell.Along with people's is to the growing interest of hygiene and health, and the consumer has proposed query to the possible cross-infection situation of washing machine.The expert in Disease Control and Prevention in China field carries out the special project investigation to Beijing area washing machine sanitary conditions; The survey showed that for it; Total number of bacteria on average reaches 13962/milliliter in the daily washings of washing machine, and it is higher than 300/square lis of national public sanitary place articles for use standards far away.The disease prevention and control center, Shanghai finds that to the domestic full-automatic turbine washing machine casual inspection in area, Shanghai City the sanitary condition in the washing machine tank is troubling, and the Escherichia coli recall rate is 100%; The mould recall rate is 60.2%; The bacterium exceeding standard rate is 81.3%, more than the washing machine that exceeds standard simultaneously of three indexs account for 54.7%, and laundry is long more service time; Inner bacteria breed must be many more, and is just more severe to the pollution of clothing.
To this situation, people have taked the multiple technologies measure to realize the antibiotic degerming of washing machine.For example; CN03262046 relates to a kind of antiseptic disinfecting washing machine, and this washing machine is equipped with ozone generator on its instrument calibration face, when opening the power switch of ozone generator; Ozone generator is exported a large amount of ozone minute bubbles; Through ozonizer directly with washing tub in contact with clothing, collision, concussion, to reach clean clothing, the difunctional effect of reach antibiotic again, sterilizing clothing.Because ozone bubbles can not fully contact with clothing, bactericidal effect is restricted.CN200920302937 discloses a kind of washing machine, and a silver ion generating means and a cover blue emission device are set in its washing drum.After silver ion receives the blue light illumination of CF; Silver ion is by catalysis; It through in water, form behind a series of chemical reaction and the physical reactions can remove simultaneously a large amount of bacteriums and fungi-OH, thereby bacterium and fungi attached to clothing are effectively killed.
CN200480000967.4 discloses a kind of antibiotic plastic composition, is by iso thiazolinium compound, the bactericidal composition that inorganic compound, silver compound are formed, and its mixing added to inside and outside the washing machine in the stave wood material, process washing machine with antibacterial functions parts.This technology does not reach the degerming index request of current GB GB21551.5-2010.
Except the above physical sterilization of mentioning with the material antimicrobial technology, combine washing machine to adopt clothing bacteria-removing liquid or thimerosal to carry out exactly in the market to the method for the direct degerming of clothing.For example " 84 thimerosal ", its main component is a clorox, and its bactericidal action mainly is to rely on its oxidability, and its shortcoming is a less stable, causes easily also during high concentration that metal gets rusty and is with the look article to fade." dew " and the main active ingredient of " Wei Lushi " all are parachlorometaxylenols; The main effect of " dripping and revealing " is to kill pathogenic entero becteria, pyococcus and pathogenic saccharomycete etc.; And " Wei Lushi " indicates and can effectively kill multiple common virus, fungi, bacterium; Belong to phenolic disinfectant owing to belong to together, the bacterium that the two was directed against is roughly the same.The parachlorometaxylenol chemical stability is good, is a kind of antimildew and antibacterial agent of safe, efficient, wide spectrum, and to most Gram-positives, negative bacterium, fungi, mould are all killed effect, and be non-stimulated, is a kind of hypotoxicity antibacterial agent.Yet people query to the safety of this material, think " be the thimerosal of primary raw material with the parachlorometaxylenol; its in the process of using because the water-fast characteristic of its sterilization component; very easily in the process of using, form phenol, and phenol is a kind of high carcinogen of generally acknowledging in the world, not only skin, mucous membrane is had corrosiveness; can also cause chronic poisoning, and causes environmental pollution ".
In addition, use in the market contain phenol or the chlorine-containing disinfecting bacteria-removing liquid all is pure organic component, degerming efficient is very high, but actual effect is shorter, all is disposable basically, the clothing of handling does not have lasting bactericidal and bacteriostatic effect.Yet use maximum anti-biotic materials in the market with long-acting performance; For example argentiferous, containing inorganic antiseptic such as zinc (like CN200310110093.5,200410010782.3,200910156604.4,200910156605.9 etc.), that pressing down of common harmful germ killed efficient is on the low side; General contact competence exertion effect in 4-8 hour is so can not satisfy the demand of quick-acting clothing degerming.
At present, need all the time a kind of safe, efficient, quick-acting, long-acting, can and the clothing bacteria-removing liquid product that is used in combination of car washing installation (like washing machine), need a kind of clothing bacteria-removing liquid preparation method simple to operate, lower-cost.For this reason, the inventor has accomplished the present invention finally through a large amount of tests.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of clothing bacteria-removing liquid.
Another object of the present invention provides the preparation method of said clothing bacteria-removing liquid.
[technical scheme]
The present invention realizes through following technical proposals.
The present invention relates to a kind of clothing bacteria-removing liquid.The composition of said clothing bacteria-removing liquid is following:
Organic antibacterial agent 20-40 weight portion;
Mesoporous silicate loaded with nano silver antibacterial agent suspension 15-20 weight portion;
Chelating anchoring stabilizing agent 0.1-0.5 weight portion;
Softener 0.1-5.0 weight portion;
Thickener 0.01-0.5 weight portion;
Emulsifier 3-8 weight portion;
Water 40-50 weight portion;
Described organic antibacterial agent is that one or more are selected from the two (C of chlorination
8～C
14) antibacterial agent of Dimethyl Ammonium, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 3-iodo-2-propynyl butyl carbamate, polyhexamethylene guanide phosphate or 1-nitrogen oxidation-2-mercaptopyridine zinc salt;
Described mesoporous silicate loaded with nano silver antibacterial agent suspension adopts following method to prepare:
(1) the meso-hole structure silicate powder was at room temperature carried out activation processing 8-12 hour with 2-10N strong acid; Its silicate powder and strong acid weight ratio 1-4; Water cleans 2-4 time repeatedly then; Neutralize with 8-12% sodium hydroxide solution by weight, make its pH value reach 6.8-7.2, centrifugation obtains active mesoporous silicate then;
(2) add mesoporous silicate of the said activity of 30-40 weight portion and 50-70 weight parts water in the homogenizer, after stirring 0.5-1.0h, obtain the mesoporous silicate solutions of a kind of activity;
(3) splash into 20-30 weight portion nano silver colloidal sol in the active mesoporous silicate solutions that step (2) obtains, stir 1.0-2.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
A preferred embodiment of the invention, described mesoporous silicate is natural zeolite or natural diatomaceous earth.
According to another kind of preferred implementation of the present invention, described strong acid is nitric acid, sulfuric acid or hydrochloric acid.
According to another kind of preferred implementation of the present invention, described nano silver colloidal sol is a Mi Youse nano silver sol in colourless nano silver colloidal sol of average grain diameter 5-10 nanometer or the average grain diameter 20-30.
According to another kind of preferred implementation of the present invention, described clothing bacteria-removing liquid is formed as follows:
Organic antibacterial agent 34-36 weight portion;
Mesoporous silicate loaded with nano silver antibacterial agent suspension 16-18 weight portion;
Chelating anchoring stabilizing agent 0.2-0.4 weight portion;
Softener 1.0-3.5 weight portion;
Thickener 0.1-0.4 weight portion;
Emulsifier 4-6 weight portion;
Water 35-45 weight portion.
According to another kind of preferred implementation of the present invention, described chelating anchoring stabilizing agent is one or more chelating anchoring stabilizing agents that are selected from sodium carboxymethyl starch, sodium carboxymethylcellulose or PVPP.
According to another kind of preferred implementation of the present invention, described softener is one or more softeners that are selected from modified polyorganosiloxane, cation organosilicon or two ethyl palmitate based quaternary ammonium salts.
According to another kind of preferred implementation of the present invention, described thickener is one or more thickeners that are selected from polyethylene glycol stearate diester, polyvinyl alcohol, cocoanut fatty acid diethanolamide or common salt.
According to another kind of preferred implementation of the present invention, described emulsifier is one or more emulsifier that are selected from polyethylene glycol, polypropylene glycol PPG400, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or fatty alcohol and ethylene oxide condensate.
The invention still further relates to a kind of preparation method of clothing bacteria-removing liquid.
The step of this method is following:
A, be added to the described organic antibacterial agent of 20-40 weight portion claim 1 in the mulser, then add 3-5 weight portion emulsifier and 40-50 weight parts water, under agitation carry out emulsification and disperse 0.5-2.0h, obtain a kind of stable microemulsion liquid;
B, be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 15-20 weight portion claim 1 in steps A) in the microemulsion that obtains, stir 0.5-1.5h after, add 0.1-0.5 weight portion chelating anchoring stabilizing agent, stir 0.4-0.8h again; Then add 0.6-5.0 weight portion softener and 0.01-0.5 weight portion thickener, continue to stir 0.1-0.8h, obtain described clothing bacteria-removing liquid.
Below the present invention will be described in more detail.
The present invention relates to a kind of clothing bacteria-removing liquid.The composition of said clothing bacteria-removing liquid is following:
Organic antibacterial agent 20-40 weight portion;
Mesoporous silicate loaded with nano silver antibacterial agent suspension 15-20 weight portion;
Chelating anchoring stabilizing agent 0.1-0.5 weight portion;
Softener 0.1-5.0 weight portion;
Thickener 0.01-0.5 weight portion;
Emulsifier 3-8 weight portion;
Water 40-50 weight portion.
At present; The normally used organic antibacterial agent of people for example is organic antibacterial agents such as phenols, organic mercury salt, organic tin salt, amide-type, thiocyanation compound, quaternary ammonium salts, biguanides; These antibacterial agents press down efficient height extremely to microorganism; Particularly fungi, mould etc. is had well to press down and kills effect, but they all exist to some extent toxicity, poor heat resistance, facile hydrolysis, service life short, be prone to produce defective such as microorganism drug resistance.So through a large amount of tests, filtering out repeatedly in earnest, the inventor has safe, efficient, long-acting organic antibacterial agent.
According to the present invention, described organic antibacterial agent is that one or more are selected from the two (C of chlorination
8～C
14) antibacterial agent of Dimethyl Ammonium, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 3-iodo-2-propynyl butyl carbamate, polyhexamethylene guanide phosphate or 1-nitrogen oxidation-2-mercaptopyridine zinc salt.
Two (the C of chlorination
8～C
14) Dimethyl Ammonium is water white thick liquid; Have two carbochains; Can produce attraction and the penetration that surpasses general disinfectant molecule far away; Can be penetrated into and kill cause of disease in the organism, under low concentration, have the superpower poisoning bacterium ability of going out, can quick and durable, efficiently kill pathogenic microorganismss such as the interior bacterium of feed lot, virus, fungi.Two (the C of the chlorination that the present invention uses
8～C
14) Dimethyl Ammonium is the product that the strong plain Pharmaceutical Technology Co., Ltd in Chengdu industry development Co., Ltd of HTC of section or Beijing produces.
The CAS numbering of 5-chloro-2 methyl-4 isothiazoline-3 ketone (CIT) and 2-methyl-4-isothiazoline-3-ketone (MIT) is 26172-55-4/2682-20-4; Little yellow transparent liquid; These two kinds of compounds usually use by weight 3: 1 mixed, external trade name " KATHON CG " (Ka Song and Kai Song).They are safe, efficient, the broad spectrum activity anticorrosion and bactericidal agents of generally acknowledging in the world; Do not contain any heavy metal and aldehydes; Can effectively suppress and go out except that mushroom and various microorganism, bacteria growing inhibiting fully under 150ppm concentration can suppress saccharomycete and fungus growth fully under 125ppm concentration.Do not contain formaldehyde, environmental protection prolongs shelf life of products greatly and improves product quality.What the present invention used is the product that Shandong moral oil blackeite worker Co., Ltd or Beijing Tianqing Chemical Co., Ltd. produce.
The CAS of 3-iodo-2-propynyl butyl carbamate (IPBC) is numbered 55406-53-6; White crystalline powder; Belong to a kind of cosmetics organic bactericide commonly used, have broad spectrum antibiotic activity, especially mould, saccharomycete and algae are had very strong inhibitory or killing effect.Because of having higher safety, can be used in the products such as cream frost, emulsion.The IPBC that the present invention uses is that the product that imperial chemical industry Co., Ltd produces is converged in Hangzhou ten thousand scape Materials Co., Ltd or Shanghai.
The CAS of polyhexamethylene guanide phosphate (PIIMG) is numbered 89697-78-9, and colourless transparent liquid belongs to organic guanidine series bactericidal agent, has good bactericidal effect, long-term bacteriostasis, and it is low, safe in utilization etc. that various metal materials are not had burn into toxicity.The PIIMG antibacterial agent that the present invention uses is the product that Guangzhou high dimerization worker Co., Ltd or the big gram of Qingdao gram biochemical technology Co., Ltd produce.
The CAS of 1-nitrogen oxidation-2-mercaptopyridine zinc salt (ZPT) is numbered 13463-41-7, and white emulsion has stronger killing power to fungi and bacterium.The ZPT antibacterial agent that the present invention uses is the product that Guangzhou high dimerization worker Co., Ltd or YiXing Liaoyuan Chemical Co., Ltd. produce.
In the present invention, described mesoporous silicate loaded with nano silver antibacterial agent suspension adopts following method to prepare:
(1) the meso-hole structure silicate powder was at room temperature carried out activation processing 8-12 hour with 2-10N strong acid; Its silicate powder and strong acid weight ratio 1-4; Water cleans 2-4 time repeatedly then; Neutralize with 8-12% sodium hydroxide solution by weight, make its pH value reach 6.8-7.2, centrifugation obtains active mesoporous silicate then;
(2) add mesoporous silicate of the said activity of 30-40 weight portion and 50-70 weight parts water in the homogenizer, after stirring 0.5-1.0h, obtain the mesoporous silicate solutions of a kind of activity;
(3) splash into 20-30 weight portion nano silver colloidal sol in the active mesoporous silicate solutions that step (2) obtains, stir 1.0-2.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
According to the regulation of IUPAC (IUPAC), mesoporous material is meant the polyporous materials of aperture between 2-50nm.Mesoporous material has characteristics such as high specific surface area, regular pore passage structure, narrow pore-size distribution, pore size is adjustable continuously; Make it in macromolecular absorption, separation, especially catalytic reaction that a lot of micro-pore zeolite molecular sieves are difficult to accomplish, play a role.And; The orderly duct of this material can be used as " microreactor "; Assembling therein has behind uniform and stable " object " material of nanoscale and becomes " Subjective and Objective material ", because the small-size effect that it is main, the Subjective and Objective effect between object and guest materials possibly have, quantum size effect etc. will make it to be expected to be widely used in technical fields such as electrode materials.At natural world two types of important silicate materials with natural meso-hole structure being arranged is zeolite and diatomite; Both distributions are very wide; Have performances such as adsorptivity, ion exchangeable, catalysis and acidproof heat-proof; Therefore be widely used as adsorbent, ion-exchanger and catalyzer, also can be used for the aspects such as drying, purification and waste water treatment of gas.
In the present invention, described mesoporous silicate is natural zeolite or natural diatomaceous earth.Natural zeolite is one type of silicates mineral that distribution is very wide.Be made up of silicon-oxy tetrahedron that links together through shared oxygen and the three-dimensional screen work of aluminum-oxygen tetrahedron, trivalent aluminium replaces the metal cation of the superfluous negative electrical charge of tetravalence silicon generation by monovalence or divalence, is generally alkali metal or alkaline earth metal cation institute balance.Natural diatomaceous earth is made up of unbodied SiO2, and contains small amount of Fe 2O3, CaO, MgO, Al2O3 and organic impurities.It is light yellow or light grey usually, matter is soft, porous, than bigger serface, relatively Incoercibility and good chemical stability.
The natural zeolite that the present invention uses is to originate from the natural zeolite powder that brilliant garden, Shijiazhuang zeolite factory produces, and the natural diatomaceous earth that the present invention uses is the diatomite that originates from the Linjiang.
Preferably, meso-hole structure silicate used in the present invention is natural zeolite.
The meso-hole structure silicate powder needs at room temperature to carry out activation processing 8-12 hour with strong acid; If the activation processing time was less than 8 hours; Can cause the mesoporous material perforate insufficient; Influence performances such as its adsorptivity, ion exchangeable, catalysis and acidproof heat-proof, all influential to anti-microbial property, the stability of the material that makes at last; If the activation processing time greater than 12 hours, is then caused time waste, production efficiency is low.Therefore the preferred said activation processing time is 10 hours.
Described strong acid is nitric acid, sulfuric acid or hydrochloric acid, preferably nitric acid.The concentration of the strong acid that uses is not very crucial, and normally 2-10N is certainly higher or low.
In the present invention, described homogenizer be that a kind of slurry shape raw material that is primarily aimed at different viscosities is pulverized, dispersion, emulsification, the efficient mixing plant of the employed routine of mixing.In the present invention; Using this equipment mainly is to let nano silver colloidal sol and mesoporous silicate material realize high velocity impact; Nano-Ag particles is penetrated in the duct of mesoporous material; And form firm associative key by some active groups in Impact energy combination and zeolite or silicate duct, load to inorganic mesoporous material and get on.The homogenizer that the present invention uses is the HTD3070 constant speed agitator (0-18000r/min) produced of the already sensible experimental instrument and equipment Co., Ltd of NGJ-3 type homogenizer (4000-12000r/min), Beijing Road that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces etc.
Inorganic carrier silver-loaded antibacterial agent is that the widest antibacterial agent is used in current antibiotic functional material field, and its anti-microbial property is efficient, safety, stable.For example CN02129700 discloses a kind of stilbite carrier zine series inorganic germicide, CN200610152032 and discloses a kind of silver supported ammonium modified nano zeolite antibacterial agent, CN200710032549.9 and disclose the antibiotic paper of a kind of inorganic zeolite with carrying silver, " chemistry world " 2005 12 phases " research of silver molecular sieve antibacterial agent ", " New Chemical Materials " 2011 the 08th phases and " carry the preparation and the anti-microbial property research thereof of silver-colored diatomite anti-biotic material " etc.No matter in these public reported is the zeolite Ag-carried antibacterial; Still diatomite carries the antibacterial agent of silver; It all adopts metal silver salt (Ag+) in the preparation, accomplishes through the ion exchange route, and it is poor that silver ion discharges the back photo and thermal stability; Oxygen in the ingress of air or run under other active substances, particularly high temperature easy to change.The present invention is when preparation mesoporous material silver-loaded antibacterial agent; Adopt nano silver colloidal sol to replace metal silver salt (Ag+), make that the preparation process is simpler, and the antibacterial activity of resultant product is stronger; Performance is more stable, has particularly effectively controlled the problem of silver-colored variable color.
Nano Silver (Nano Silver) is that particle diameter is nano level argent simple substance.Discover that Nano Silver is the bactericide stronger than antibiotic, can directly kill 650 various bacteria rapidly, make its forfeiture fertility; Permeability is strong, can promote wound healing, cell growth and damaged cell reparation; Antibiotic lasting, safety non-toxic does not have any IR to skin yet; Characteristics such as have no drug resistance.
According to the present invention, described nano silver colloidal sol is that to select average grain diameter be the colourless nano silver colloidal sol (argentiferous 10000ppm) of 5-10 nanometer or coloured nano silver sol (argentiferous 10000ppm) that average grain diameter is the 20-30 nanometer to described nano silver colloidal sol; The nanoparticle features of the selected Nano Silver of the present invention is seen accompanying drawing 1 and accompanying drawing 2 transmission electron microscope photos.
Preferably, described nano silver colloidal sol is a kind of coloured nano silver colloidal sol.The nano silver colloidal sol that the present invention uses is to produce according to the applicant's ZL200910091031 patented technology, and its average grain diameter is the 20-30 nanometer, and product appearance is light yellow transparent homogeneous liquid.The colourless nano silver colloidal sol of 5-10 nanometer is the product that Korea S NANUX company produces.
In the present invention; When the amount of organic antibacterial agent is the 20-40 weight portion; The amount of mesoporous silicate loaded with nano silver antibacterial agent suspension is the 15-20 weight portion, if the amount of mesoporous silicate loaded with nano silver antibacterial agent suspension is lower than 15 weight portions, then can influence the degerming performance of clothing bacteria-removing liquid; If the amount of mesoporous silicate loaded with nano silver antibacterial agent suspension is higher than 20 weight portions, also can cause clothing bacteria-removing liquid degerming performance not ideal enough, perhaps active ingredient waste.Preferably, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of mesoporous silicate loaded with nano silver antibacterial agent suspension was the 16-18 weight portion.
According to the present invention; Chelating anchoring stabilizing agent should be appreciated that it is a kind of its cubic network structure of utilizing; Make nano silver colloidal sol particle and organic antibacterial agent be securely fixed in the chemical substance in the meso-hole structure silicate duct; Therefore every have this performance and do not damage any chemical substance of clothing bacteria-removing liquid character of the present invention again and may be used to the present invention, also all in protection scope of the present invention.
In the present invention, described chelating anchoring stabilizing agent is one or more chelating anchoring stabilizing agents that are selected from sodium carboxymethyl starch (CMS), sodium carboxymethylcellulose (CMC) or PVPP (PVPP).They have water absorption and swelling and form the performance of 3 D cross-linked network, have multiple performances such as thickening, suspension, dispersion, emulsification, bonding, water conservation, protecting colloid.The present invention utilizes their these performances, and nano silver colloidal sol particle and organic antibacterial agent are securely fixed in the meso-hole structure silicate duct.The sodium carboxymethyl starch (CMS) that the present invention uses is that the product that chemical industry Co., Ltd produces is contained in Yantai forever; Sodium carboxymethylcellulose (CMC) is the product that the happy chemical industry of prestige (Suzhou) Co., Ltd produces; PVPP (PVPP) is that Jiaozhuo U.S.A reaches the product that fine chemistry industry Co., Ltd produces.
In the present invention, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of chelating anchoring stabilizing agent was the 0.1-0.5 weight portion, if the amount of chelating anchoring stabilizing agent is lower than 0.1 weight portion, then can influence the shelf stability of clothing bacteria-removing liquid, shortened memory time; If the amount of chelating anchoring stabilizing agent is higher than 0.5 weight portion, thereby then can causes the abuse of stabilizing agent and possibly have influence on the loss that clothing bacteria-removing liquid content of effective causes performance.Preferably, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of chelating anchoring stabilizing agent was the 0.2-0.4 weight portion.
According to the present invention; Softener should be appreciated that it is that a kind of reduction of fabric fibre coefficient of friction, mobility of can making strengthens; Make fabric soft, fluffy, the resilient more any chemical substance that becomes; Therefore every have this performance and do not damage any chemical substance of clothing bacteria-removing liquid character of the present invention again and may be used to the present invention, also all in protection scope of the present invention.
Described softener is one or more softeners that are selected from modified polyorganosiloxane, cation organosilicon or two ethyl palmitate based quaternary ammonium salts.The for example modified polyorganosiloxane produced of Clariant chemical industry (China) Co., Ltd, two ethyl palmitate based quaternary ammonium salts that Sha Suo Chemical Industry Science Co., Ltd in Guangzhou produces.
In the present invention; When the amount of organic antibacterial agent was the 20-40 weight portion, the amount of softener was the 0.1-5.0 weight portion, if the amount of softener is lower than 0.1 weight portion; Then can not effectively eliminate and use clothing bacteria-removing liquid washing back clothing feel bad, be prone to produce harmful effects such as static; If the amount of softener is higher than 5.0 weight portions, then can cause softener to use waste, and the content that influences the effective degerming composition of product.Preferably, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of softener was the 1.0-3.5 weight portion.
According to the present invention; Thickener should be appreciated that it is a kind ofly the material viscosity is improved or form gel; Thereby change its material physical behavior; Also have emulsification, stable or make the chemical substance that is the suspended state effect, therefore every have this performance and do not damage any chemical substance of clothing bacteria-removing liquid character of the present invention again and may be used to the present invention, also all in protection scope of the present invention.
Described thickener is one or more thickeners that are selected from polyethylene glycol stearate diester, polyvinyl alcohol, cocoanut fatty acid diethanolamide or common salt.Polyethylene glycol stearate diester, polyvinyl alcohol, cocoanut fatty acid diethanolamide are the product that the great first Science and Technology Ltd. in Tianjin produces; Common salt (NaCl) is buied for extensive and profound in meaning star chemical reagent shop, Beijing.
In the present invention, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of thickener was the 0.01-0.5 weight portion, if the amount of thickener is lower than 0.01 weight portion, then can reduce the viscosity of bacteria-removing liquid, caused the bacteria-removing liquid system unstable, easily deposition; If the amount of thickener is higher than 0.5 weight portion, then can make bacteria-removing liquid viscosity too high, influence the flowability of bacteria-removing liquid.Preferably, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of thickener was the 0.1-0.4 weight portion.
According to the present invention; Emulsifier should be appreciated that it is a kind of interfacial tension that can reduce between non soluble liquids; Make it to form the material of emulsion; Therefore every have this performance and do not damage any chemical substance of clothing bacteria-removing liquid character of the present invention again and may be used to the present invention, also all in protection scope of the present invention.
Described emulsifier is one or more emulsifier that are selected from polyethylene glycol (PEG200), polypropylene glycol PPG400, sorbitan fatty acid ester (Span-60), polyoxyethylene sorbitan fatty acid ester (Tween-80) or fatty alcohol and ethylene oxide condensate (paregal O-20), and they are products that companies such as Jiangsu "four news" (new ideas interfacial agents Science and Technology Ltd., the great first Science and Technology Ltd. in Tianjin produce.
In the present invention, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of emulsifier was the 3-8 weight portion, if the amount of emulsifier is lower than 3 weight portions, then good emulsification organic antibacterial agent causes the bacteria-removing liquid system unstable; If the amount of emulsifier is higher than 8 weight portions, then can cause the waste of emulsifier.Preferably, when the amount of organic antibacterial agent was the 20-40 weight portion, the amount of emulsifier was the 4-6 weight portion.
The invention still further relates to a kind of preparation method of clothing bacteria-removing liquid.
The step of this method is following:
A, be added to 20-40 weight portion such as foregoing organic antibacterial agent in the mulser, then add 3-5 weight portion emulsifier and 40-50 weight parts water, under agitation carry out emulsification and disperse 0.5-2.0h, obtain a kind of stable microemulsion liquid.
Described mulser is a kind ofly can a phase or a plurality of phase be distributed to the equipment in another continuous phase quickly and evenly.Because high tangential velocity that the rotation of mulser rotor high-speed is produced and high frequency machinery effect belt come powerful kinetic energy; Make that material receives strong machinery and fluid power shearing, centrifugal extruding, liquid layer friction in the narrow gap of stator and rotor, bump is torn and comprehensive function such as turbulent flow; Thereby make immiscible solid phase, liquid phase, gas phase even dispersion and emulsion of moment, obtain a kind of stable microemulsion liquid.The used high-shear emulsion machine of the present invention is a high-shearing dispersion emulsifying machine at the bottom of the 100L still produced of Nantong Clare's mixing apparatus Co., Ltd, and its maximum line velocity can reach 40m/s.
Described high-shear emulsion machine is in the process of the described clothing bacteria-removing liquid of preparation; Its mixing speed is controlled at 1000-3000rpm; Be about to the blade linear velocity and be controlled at 10-40m/s, cross low or too high blade linear velocity and do not help forming the stable inorganic/organic composite antibiotic agent system that meets the requirements.Certainly, also can use the emulsifier of other model to stir, but need satisfy the requirement of blade linear velocity.
B, be added to 15-20 weight portion such as foregoing mesoporous silicate loaded with nano silver antibacterial agent suspension in steps A) in the microemulsion that obtains, stir 0.5-1.5h after, add 0.1-0.5 weight portion chelating anchoring stabilizing agent, stir 0.4-0.8h again; Then add 0.6-5.0 weight portion softener and 0.01-0.5 weight portion thickener, continue to stir 0.1-0.8h, obtain described clothing bacteria-removing liquid.
Wherein said emulsifier, mesoporous silicate loaded with nano silver antibacterial agent suspension, chelating anchoring stabilizing agent, softener and thickener such as noted earlier repeat no more.
Clothing bacteria-removing liquid of the present invention can be used for the washing machine washing clothes; Washing machine washing 5kg clothing only need use the 0.5-1mL bacteria-removing liquid; According to GB21551.5-2010 " antibiotic, the degerming of household electrical appliances and similar applications electrical equipment, the specific (special) requirements of purification function washing machine ", the degerming rate can reach more than 99%; 1kg hand washing clothing adds the 0.2mL bacteria-removing liquid in rinse cycle, soaked then 10 minutes, and clothing degerming rate is also up to more than 99%.
Clothing bacteria-removing liquid of the present invention is not more than 15ppm to the minimal inhibitory concentration of Escherichia coli ATCC 25922 and staphylococcus aureus ATCC6538P.
Specify the clothing bacteria-removing liquid Performance Detection test of the present invention's preparation below.
Detection method and testing result are following.
The minimal inhibitory concentration test (MIC) of A, clothing bacteria-removing liquid of the present invention:
2.1.7.3 makes an experiment according to Ministry of Public Health's disinfection technology standard (version in 2002), and its result of the test is listed in the table 1.
The minimal inhibitory concentration result of the test of table 1 clothing bacteria-removing liquid
| Project | Escherichia coli ATCC 25922 | Staphylococcus aureus ATCC 6538P |
| MIC/ppm | 13 | 10 |
B, clothing bacteria-removing liquid organic antibacterial agent and inorganic nano silver antibacterial agent are re-dubbed synergistic mensuration between the branch:
At first use the method for the test minimal inhibitory concentration that A mentions, the minimal inhibitory concentration of test one-component, its result of the test is listed in the table 2; And then respectively organic antibacterial agent and inorganic nano silver antibacterial agent are mixed by 1: 1 proportioning, adopt the method for the test minimal inhibitory concentration that A mentions equally, test the minimal inhibitory concentration of composite component.Each component is done the mother liquor that solvent dilution becomes 10000ppm with ethanol-water solution (1: 1) respectively, and each component concentrations also all is 10000ppm in the mixed liquor.
This test with reference to antibiotic synergy classification Mlc index method commonly used (fractional inhibitory concentration FIC) estimates the antibiotic synergistic function of its organic antibacterial agent and inorganic antiseptic compounding ingredients.
The computing formula of FIC index is:
The part Mlc (FIC) that calculates two composite compositions according to above formula is to judge the interaction between them.Two component lists are at present for collaborative when FIC≤0.5, and 0.5＜FIC≤1 o'clock is stack, and 1＜FIC＜2 o'clock are uncorrelated, and FIC>=2 o'clock are antagonism.Its result of the test is listed in the table 3.
Table 2 antibacterial agent list composition is to the minimal inhibitory concentration (MIC) of bacterium
The composite composition of table 3 antibacterial agent is to the minimal inhibitory concentration (MIC) of bacterium
And be re-dubbed the classification Mlc index (FIC) between the branch
General material can be regarded as less than 800ppm the minimal inhibitory concentration of bacterium has anti-microbial property, must be less than 800ppm like the minimal inhibitory concentration of regulation among the industry standard HG/T3794-2005 " inorganic antiseptic-performance and evaluation ".Minimal inhibitory concentration (MIC) result by the single antibacterial components of table 2 can find out that the minimal inhibitory concentration of the selected antibacterial agent component of the present invention all is far smaller than 800ppm, so all showed good bacteriostatic activity.Table 3 shows, and compares as the time spent separately, and the minimal inhibitory concentration of composite back antibacterial agent system composition all reduces more.Judge the interaction between organic antibacterial agent and the inorganic antiseptic composite parts according to classification Mlc index method: as far as two kinds of bacteriums; The FIC index of selected organic antibacterial agent and inorganic antiseptic composite parts is all less than 1; The selected composite parts of this explanation the present invention all has Synergistic or superposition, does not exist uncorrelated or antagonism; In all combinations; (C8～C14) Dimethyl Ammonium/coloured Nano Silver (to colibacillary FIC=0.82), card pine are (CIT/ (MIT)/coloured Nano Silver (to the FIC=0.62 of staphylococcus aureus), the coloured Nano Silver of PHMG/ (to colibacillary FIC=0.52) except chlorination is two; The FIC of all the other sample tests all is less than or equal to 0.5; That is to say that all the other combinations all show as synergistic function except above listed three combinations show as the effect stack, and the FIC index of colourless Nano Silver combination Escherichia coli of PHMG/ and staphylococcus aureus is respectively 0.14 and 0.18; Numerical value is minimum, and synergistic function is the strongest.
C, clothing bacteria-removing liquid effect of the present invention evaluation test in washing machine:
Use the washing machine of no antibiotic function usually; Experimental arrangement according to GB21551.5-2010 " antibiotic, the degerming of household electrical appliances and similar applications electrical equipment, the specific (special) requirements of purification function washing machine " appendix A A regulation; Carry out interpolation clothing bacteria-removing liquid of the present invention and do not added clothing bacteria-removing liquid of the present invention " washing-degerming test " comparative trial; Washing clothes is 5kg, and the clothing bacteria-removing liquid quantity of adding is 0.5mL, and its result of the test is listed in the table 4.
The clothing degerming result of the test that table 4 carries out on washing machine
The antibiotic washing resistance performance test of the clothing that D, use clothing bacteria-removing liquid of the present invention are handled
This test is with reference to the washing procedure of FZ/T 73023-2006 " antibiosis knitting article appendix C antibiotic fabric sample decantation test method ", and its result of the test is listed in the table 5.
The clothing that table 5 is handled through bacteria-removing liquid is washed the antibacterial effect after 20 times
The acute oral toxicity test of E, clothing bacteria-removing liquid
Test method according to standard ISO 10993-11:2006 regulation is carried out, and experimental animal is the rat of 180-220g, and its result of the test is listed in the table 6.
The security performance test result of table 6 clothing bacteria-removing liquid
F, skin irritation test
Test method according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.3.3 regulation is carried out, and experimental animal is the NZw of 2.13-2.69kg, and result of the test shows nonirritant, and its result of the test is listed in the table 6.
The above results clearly illustrates that; The special-purpose clothing bacteria-removing liquid of the washing machine that uses the present invention to prepare is not more than 15ppm to the minimal inhibitory concentration of Escherichia coli ATCC 25922 and staphylococcus aureus ATCC 6538P; The minimal inhibitory concentration of common efficient silver base inorganic antibacterial agent is at 150-600ppm, so can find out that the clothing bacteria-removing liquid bacteriostatic activity that the present invention prepares is high more a lot of than common inorganic antiseptic; The clothing bacteria-removing liquid of the present invention preparation adds degerming rate to clothing greater than 99% with the washing machine washing clothes time; The clothing of handling simultaneously after water washing 20 times antibiotic rate itself still greater than 90%; This explanation clothing clothing self after bacteria-removing liquid is handled can keep pressing down of a period of time to kill effect to bacterium, has good antibiotic endurance quality; Acute oral toxicity test to the clothing bacteria-removing liquid belongs to actual nontoxic; Skin irritation belongs to nonirritant; And general pure organic type of antibacterial agent bactericide all has certain toxicity and skin irritation; Can not satisfy actual use needs,, can relievedly use so the clothing bacteria-removing liquid of explanation the present invention preparation is safe.
To compare the test explanation to common in the market laundry degerming disinfectant and clothing bacteria-removing liquid of the present invention below.
Use sell on the market at home to clothing carry out the degerming sterilization product 84 thimerosals, drip the washing machine special use clothing bacteria-removing liquid that reveals clothing bacteria-removing liquid and Wei Lushi clothing bacteria-removing liquid and the present invention's preparation; Under same condition, carried out the performance comparison test; It is Escherichia coli (ATCC25922) that used bacterial classification is tested in antibiotic degerming, and handling procedure and evaluation of degerming antibacterial effect and top description is identical.Comparative evaluation's result of the test is listed in table 7.
The comparative trial effect of several kinds of clothing bacteria-removing liquids of table 7
Can find out from table 7 comparative test result; With on the present domestic market commonly used to clothing carry out the degerming sterilization product 84 thimerosals, drip and reveal a clothing bacteria-removing liquid and compare with Wei Lushi clothing bacteria-removing liquid; Under similarity condition; Be equal to or be lower than under the condition of other product adding proportions, the special-purpose clothing bacteria-removing liquid of the washing machine bacteria-eliminating efficacy of the present invention's preparation is equal to or is superior to other products, is particularly showing good durable antibacterial effect aspect the water-fast washing; Antibiotic rate is still greater than 90% after washing 20 times, and other three series products all do not have this effect; All be equal to or be superior to other three series products aspect skin thorn property and the maintenance clothing good appearance color in addition.
[beneficial effect]
The present invention has following beneficial effect:
Clothing bacteria-removing liquid of the present invention is safe to use, and the clothing degerming reaches more than 99%, and stability is good; The antibiotic rate of clothing itself still reaches more than 90% after water washing 20 times, has good antibiotic endurance quality, and is nontoxic; To the skin nonirritant, fabric had the deodorizing odor-resistant result.The production technology of clothing bacteria-removing liquid of the present invention is simple, and equipment investment is few, is easy to suitability for industrialized production, and is environmentally friendly, has the very strong market competitiveness.
[description of drawings]
Fig. 1 is the transmission electron microscope figure (TEM) of colourless nano silver colloidal sol of the present invention;
Fig. 2 is the transmission electron microscope figure (TEM) of coloured nano silver colloidal sol of the present invention.
[embodiment]
To understand the present invention better through following these embodiment.
Embodiment 1: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) natural zeolite powder (average grain diameter is less than 0.5 μ m) of brilliant garden, Shijiazhuang zeolite factory production at room temperature carried out activation processing 10 hours with 6N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 1; Water cleans 3 times repeatedly then; Neutralize with 10% sodium hydroxide solution by weight, make its pH value reach 6.9, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 30 weight portions and 50 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 1h rotating speed 4000r/min under;
(3) splash into 20 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 1.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), two (the Dimethyl Ammonium organic antibacterial agent of C8～C14) is added in the mulser that Nantong Clare's mixing apparatus Co., Ltd produces 20 weight portion chlorinations; Then add 3 weight portion polyoxyethylene sorbitan fatty acid ester (Tween-80) emulsifier and 50 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 1h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 15-20 weight portion in the microemulsion that step (1) obtains, after continuing to stir 1h, add 0.3 weight portion sodium carboxymethyl starch (CMS) chelating anchoring stabilizing agent, stir 0.5h again; Then add 3.0 weight portion modified polyorganosiloxane softeners and 0.1 weight account polyethylene alcohol thickener, continue to stir 0.5h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 15ppm and 12ppm; Prepared clothing bacteria-removing liquid adds 1.0mL the degerming rate of clothing is reached 99.20% with washing machine washing 5kg clothing the time, process clothes itself is respectively 91.20% and 94.60% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Embodiment 2: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) natural zeolite powder (average grain diameter is less than 0.5 μ m) of brilliant garden, Shijiazhuang zeolite factory production at room temperature carried out activation processing 9 hours with 2N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 3; Water cleans 3 times repeatedly then; Neutralize with 10% sodium hydroxide solution by weight, make its pH value reach 7.0, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 38 weight portions and 65 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 0.8h rotating speed 1000r/min under;
(3) splash into 28 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 1.8h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), is added to 35 weight portion 5-chloro-2-methyl-4-isothiazoline-3-ketone organic antibacterial agents in the mulser of Nantong Clare's mixing apparatus Co., Ltd production; Then add 4 weight portion polyethylene glycol emulsifier and 48 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 1.6h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 18 weight portions in the microemulsion that step (1) obtains, after continuing to stir 0.8h, add 0.4 weight portion sodium carboxymethylcellulose chelating anchoring stabilizing agent, stir 0.5h again; Then add 4.0 weight portion cation organosilicon softeners and 0.1 weight portion polyethylene glycol stearate diester thickener, continue to stir 0.6h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 10ppm and 6ppm; Prepared clothing bacteria-removing liquid adds 0.5mL the degerming rate of clothing is reached 99.99% with washing machine washing 5kg clothing the time, process clothes itself is respectively 98.70% and 99.50% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Embodiment 3: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) natural zeolite powder (average grain diameter is less than 0.5 μ m) of brilliant garden, Shijiazhuang zeolite factory production at room temperature carried out activation processing 12 hours with 6N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 2; Water cleans 2 times repeatedly then; Neutralize with 9% sodium hydroxide solution by weight, make its pH value reach 6.9, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 34 weight portions and 52 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 0.6h rotating speed 2000r/min under;
(3) splash into 24 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 1.4h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), is added to 25 weight portion 2-methyl-4-isothiazoline-3-ketone organic antibacterial agent in the mulser of Nantong Clare's mixing apparatus Co., Ltd production; Then add 3 weight portion polypropylene glycol PPG400 emulsifier and 44 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 1.0h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 14 weight portions in the microemulsion that step (1) obtains, after continuing to stir 1.2h, add 0.2 weight portion PVPP chelating anchoring stabilizing agent, stir 0.6h again; Then add two ethyl palmitate based quaternary ammonium salt softeners of 2.0 weight portions and 0.3 weight portion cocoanut fatty acid diethanolamide thickener, continue to stir 0.4h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 14ppm and 10ppm; Prepared clothing bacteria-removing liquid adds 0.8mL the degerming rate of clothing is reached 99.35% with washing machine washing 5kg clothing the time, process clothes itself is respectively 90.90% and 91.30% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Embodiment 4: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) natural zeolite powder (average grain diameter is less than 0.5 μ m) of brilliant garden, Shijiazhuang zeolite factory production at room temperature carried out activation processing 10 hours with 4N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 4; Water cleans 4 times repeatedly then; Neutralize with 12% sodium hydroxide solution by weight, make its pH value reach 7.2, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 40 weight portions and 70 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 1.0h rotating speed 2000r/min under;
(3) splash into 30 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 2.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), is added to 40 weight portion 1-nitrogen oxidations-2-mercaptopyridine zinc salt organic antibacterial agent in the mulser of Nantong Clare's mixing apparatus Co., Ltd production; Then add 5 weight portion fatty alcohols and ethylene oxide condensate emulsifier and 50 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 2.0h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 20 weight portions in the microemulsion that step (1) obtains, after continuing to stir 1.5h, add 0.5 weight portion sodium carboxymethylcellulose chelating anchoring stabilizing agent, stir 0.8h again; Then add 5.0 weight portion modified polyorganosiloxane softeners and 0.5 weight account polyethylene alcohol thickener, continue to stir 0.8h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 14ppm and 15ppm; Prepared clothing bacteria-removing liquid adds 1.0mL the degerming rate of clothing is reached 99.00% with washing machine washing 5kg clothing the time, process clothes itself is respectively 91.90% and 90.50% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Embodiment 5: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) the natural diatomaceous earth powder (average grain diameter is less than 0.5 μ m) that originates from the Linjiang at room temperature carried out activation processing 10 hours with 6N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 1; Water cleans 3 times repeatedly then; Neutralize with 10% sodium hydroxide solution by weight, make its pH value reach 6.9, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 30 weight portions and 50 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 1h rotating speed 4000r/min under;
(3) splash into 20 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 1.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), is added to 20 weight portion polyhexamethylene guanide phosphate (PHMG) organic antibacterial agents in the mulser of Nantong Clare's mixing apparatus Co., Ltd production; Then add 3 weight portion polyoxyethylene sorbitan fatty acid ester (Tween-80) emulsifier and 50 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 1h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 15-20 weight portion in the microemulsion that step (1) obtains, after continuing to stir 1h, add 0.3 weight portion sodium carboxymethyl starch (CMS) chelating anchoring stabilizing agent, stir 0.5h again; Then add 3.0 weight portion modified polyorganosiloxane softeners and 0.1 weight account polyethylene alcohol thickener, continue to stir 0.5h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 8ppm and 5ppm; Prepared clothing bacteria-removing liquid adds 1.0mL the degerming rate of clothing is reached 99.99% with washing machine washing 5kg clothing the time, process clothes itself is respectively 94.50% and 98.30% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Embodiment 6: the preparation of clothing bacteria-removing liquid of the present invention
Its preparation process is following:
The preparation of A, mesoporous silicate loading nano silvery inorganic antiseptic suspension
(1) the natural diatomaceous earth powder (average grain diameter is less than 0.5 μ m) that originates from the Linjiang at room temperature carried out activation processing 12 hours with 6N nitric acid; Its natural zeolite powder and nitric acid weight ratio are 2; Water cleans 2 times repeatedly then; Neutralize with 9% sodium hydroxide solution by weight, make its pH value reach 6.9, centrifugation obtains active mesoporous silicate then;
(2) add the mesoporous silicate of the described activity of 34 weight portions and 52 weight parts waters in the NGJ-3 type homogenizer that Qingdao grand auspicious petroleum machinery Manufacturing Co., Ltd produces, obtaining the mesoporous silicate solutions of a kind of activity behind the stirring 0.6h rotating speed 2000r/min under;
(3) splash into 24 weight portion nano silver colloidal sols in the active mesoporous silicate solutions that step (2) obtains, stir 1.4h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
The preparation of B, clothing bacteria-removing liquid
(1), is added to 25 weight portion 3-iodo-2-propynyl butyl carbamate organic antibacterial agents in the mulser of Nantong Clare's mixing apparatus Co., Ltd production; Then add 3 weight portion polypropylene glycol PPG400 emulsifier and 44 weight parts waters; Under the stirring of the NGJ-3 type homogenizer that the grand auspicious petroleum machinery in Qingdao Manufacturing Co., Ltd produces, carry out emulsification and disperse 1.0h, obtain a kind of stable microemulsion liquid;
(2), be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 14 weight portions in the microemulsion that step (1) obtains, after continuing to stir 1.2h, add 0.2 weight portion PVPP chelating anchoring stabilizing agent, stir 0.6h again; Then add two ethyl palmitate based quaternary ammonium salt softeners of 2.0 weight portions and 0.3 weight portion cocoanut fatty acid diethanolamide thickener, continue to stir 0.4h, obtain described clothing bacteria-removing liquid.
Use the clothing bacteria-removing liquid of this embodiment preparation, adopt the method for describing in this specification to detect, consequently the minimal inhibitory concentration of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538P) is respectively 5ppm and 5ppm; Prepared clothing bacteria-removing liquid adds 0.8mL the degerming rate of clothing is reached 99.35% with washing machine washing 5kg clothing the time, process clothes itself is respectively 98.50% and 99.70% to the antibiotic rate of Escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC6538P) after water washing 20 times simultaneously.
Claims (10)
1. clothing bacteria-removing liquid is characterized in that the composition of said clothing bacteria-removing liquid is following:
Organic antibacterial agent 20-40 weight portion;
Mesoporous silicate loaded with nano silver antibacterial agent suspension 15-20 weight portion;
Chelating anchoring stabilizing agent 0.1-0.5 weight portion;
Softener 0.1-5.0 weight portion;
Thickener 0.01-0.5 weight portion;
Emulsifier 3-8 weight portion;
Water 40-50 weight portion;
Described organic antibacterial agent is that one or more are selected from the two (C of chlorination
8～C
14) antibacterial agent of Dimethyl Ammonium, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, 3-iodo-2-propynyl butyl carbamate, polyhexamethylene guanide phosphate or 1-nitrogen oxidation-2-mercaptopyridine zinc salt;
Described mesoporous silicate loaded with nano silver antibacterial agent suspension adopts following method to prepare:
(1) the meso-hole structure silicate powder was at room temperature carried out activation processing 8-12 hour with 2-10N strong acid; Its silicate powder and strong acid weight ratio 1-4; Water cleans 2-4 time repeatedly then; Neutralize with 8-12% sodium hydroxide solution by weight, make its pH value reach 6.8-7.2, centrifugation obtains active mesoporous silicate then;
(2) add mesoporous silicate of the said activity of 30-40 weight portion and 50-70 weight parts water in the homogenizer, after stirring 0.5-1.0h, obtain the mesoporous silicate solutions of a kind of activity;
(3) splash into 20-30 weight portion nano silver colloidal sol in the active mesoporous silicate solutions that step (2) obtains, stir 1.0-2.0h again, obtain a kind of mesoporous silicate loaded with nano silver antibacterial agent suspension.
2. clothing bacteria-removing liquid according to claim 1 is characterized in that described mesoporous silicate is natural zeolite or natural diatomaceous earth.
3. clothing bacteria-removing liquid according to claim 1 is characterized in that described strong acid is nitric acid, sulfuric acid or hydrochloric acid.
4. clothing bacteria-removing liquid according to claim 1 is characterized in that described nano silver colloidal sol is Mi Wuse nano silver colloidal sol or the interior Mi Youse nano silver sol of average grain diameter 20-30 in the average grain diameter 5-10.
5. clothing bacteria-removing liquid according to claim 1 is characterized in that described clothing bacteria-removing liquid composition as follows:
Organic antibacterial agent 34-36 weight portion;
Mesoporous silicate loaded with nano silver antibacterial agent suspension 16-18 weight portion;
Chelating anchoring stabilizing agent 0.2-0.4 weight portion;
Softener 1.0-3.5 weight portion;
Thickener 0.1-0.4 weight portion;
Emulsifier 4-6 weight portion;
Water 35-45 weight portion.
6. according to claim 1 or 5 described clothing bacteria-removing liquids, it is characterized in that described chelating anchoring stabilizing agent is one or more chelating anchoring stabilizing agents that are selected from sodium carboxymethyl starch, sodium carboxymethylcellulose or PVPP.
7. according to claim 1 or 5 described clothing bacteria-removing liquids, it is characterized in that described softener is one or more softeners that are selected from modified polyorganosiloxane, cation organosilicon or two ethyl palmitate based quaternary ammonium salts.
8. according to claim 1 or 5 described clothing bacteria-removing liquids, it is characterized in that described thickener is one or more thickeners that are selected from polyethylene glycol stearate diester, polyvinyl alcohol, cocoanut fatty acid diethanolamide or common salt.
9. according to claim 1 or 5 described clothing bacteria-removing liquids, it is characterized in that described emulsifier is one or more emulsifier that are selected from polyethylene glycol, polypropylene glycol PPG400, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or fatty alcohol and ethylene oxide condensate.
10. the preparation method of a clothing bacteria-removing liquid is characterized in that the step of this method is following:
A, be added to the described organic antibacterial agent of 20-40 weight portion claim 1 in the mulser, then add 3-5 weight portion emulsifier and 40-50 weight parts water, under agitation carry out emulsification and disperse 0.5-2.0h, obtain a kind of stable microemulsion liquid;
B, be added to the described mesoporous silicate loaded with nano silver antibacterial agent suspension of 15-20 weight portion claim 1 in steps A) in the microemulsion that obtains, stir 0.5-1.5h after, add 0.1-0.5 weight portion chelating anchoring stabilizing agent, stir 0.4-0.8h again; Then add 0.6-5.0 weight portion softener and 0.01-0.5 weight portion thickener, continue to stir 0.1-0.8h, obtain described clothing bacteria-removing liquid.
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726298A (en) * | 2013-11-26 | 2014-04-16 | 常熟常圣服饰有限公司 | Preparation technology of anti-bacterial underwear fabric |
| CN103790027A (en) * | 2013-11-30 | 2014-05-14 | 常熟市亚欧进出口贸易有限公司 | Technology for processing antibacterial insect-resistant shell fabric |
| CN105087180A (en) * | 2015-09-07 | 2015-11-25 | 龚灿锋 | Antibacterial and anti-mildew cleaning and treating agent for towels |
| CN105133316A (en) * | 2015-09-29 | 2015-12-09 | 湖北穆兰同大科技有限公司 | Fabric conditioner and preparation method thereof |
| CN105296192A (en) * | 2015-11-19 | 2016-02-03 | 黑龙江大学 | Nano silver added powerful sterilizing and lasting bacteria-resisting laundry detergent and manufacturing method therefor |
| CN105494429A (en) * | 2015-12-09 | 2016-04-20 | 中国建筑材料科学研究总院 | Antibacterial and antifungal agent, preparation method thereof and antibacterial and antifungal method |
| CN108395756A (en) * | 2018-03-07 | 2018-08-14 | 湖州光博生物科技有限公司 | A kind of nanometer silver antimicrobial glue and preparation method thereof |
| CN109811545A (en) * | 2017-11-21 | 2019-05-28 | 广州泓一生物科技有限公司 | A kind of nanogold softener and preparation method thereof |
| CN109826003A (en) * | 2019-03-09 | 2019-05-31 | 安徽云超智能科技有限公司 | A kind of underpants inorganic agent |
| CN111418607A (en) * | 2020-03-30 | 2020-07-17 | 北京机科国创轻量化科学研究院有限公司 | Composite nano-silver antiviral agent and preparation method and application thereof |
| CN111493073A (en) * | 2020-05-28 | 2020-08-07 | 李学军 | Surface disinfection film covering agent and preparation method thereof |
| 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 |
| CN111690469A (en) * | 2020-07-08 | 2020-09-22 | 青岛拜士特新材料有限公司 | Degerming washing powder containing zinc pyrithione antibacterial agent 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 |
| CN111733596A (en) * | 2020-07-20 | 2020-10-02 | 首都医科大学 | Noble metal antibacterial disinfectant, noble metal-loaded antibacterial mask and preparation method thereof |
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| CN115109665A (en) * | 2022-07-29 | 2022-09-27 | 成都汉德尔新材料有限公司 | Safe and environment-friendly disinfection and sterilization laundry detergent and preparation method thereof |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726298A (en) * | 2013-11-26 | 2014-04-16 | 常熟常圣服饰有限公司 | Preparation technology of anti-bacterial underwear fabric |
| CN103790027A (en) * | 2013-11-30 | 2014-05-14 | 常熟市亚欧进出口贸易有限公司 | Technology for processing antibacterial insect-resistant shell fabric |
| CN105087180A (en) * | 2015-09-07 | 2015-11-25 | 龚灿锋 | Antibacterial and anti-mildew cleaning and treating agent for towels |
| CN105133316A (en) * | 2015-09-29 | 2015-12-09 | 湖北穆兰同大科技有限公司 | Fabric conditioner and preparation method thereof |
| CN105296192A (en) * | 2015-11-19 | 2016-02-03 | 黑龙江大学 | Nano silver added powerful sterilizing and lasting bacteria-resisting laundry detergent and manufacturing method therefor |
| CN105494429B (en) * | 2015-12-09 | 2020-08-18 | 中国建筑材料科学研究总院 | Antibacterial mildew preventive, preparation method thereof and antibacterial mildew preventive method |
| CN105494429A (en) * | 2015-12-09 | 2016-04-20 | 中国建筑材料科学研究总院 | Antibacterial and antifungal agent, preparation method thereof and antibacterial and antifungal method |
| CN109811545A (en) * | 2017-11-21 | 2019-05-28 | 广州泓一生物科技有限公司 | A kind of nanogold softener and preparation method thereof |
| CN108395756B (en) * | 2018-03-07 | 2020-08-18 | 济南豪瑞生物技术有限公司 | Nano-silver antibacterial adhesive and preparation method thereof |
| CN108395756A (en) * | 2018-03-07 | 2018-08-14 | 湖州光博生物科技有限公司 | A kind of nanometer silver antimicrobial glue and preparation method thereof |
| CN109826003A (en) * | 2019-03-09 | 2019-05-31 | 安徽云超智能科技有限公司 | A kind of underpants inorganic agent |
| CN111418607A (en) * | 2020-03-30 | 2020-07-17 | 北京机科国创轻量化科学研究院有限公司 | Composite nano-silver antiviral agent and preparation method and application thereof |
| CN111493073A (en) * | 2020-05-28 | 2020-08-07 | 李学军 | Surface disinfection film covering agent and preparation method thereof |
| 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 |
| CN111690469A (en) * | 2020-07-08 | 2020-09-22 | 青岛拜士特新材料有限公司 | Degerming washing powder containing zinc pyrithione antibacterial agent 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 |
| CN111733596A (en) * | 2020-07-20 | 2020-10-02 | 首都医科大学 | Noble metal antibacterial disinfectant, noble metal-loaded antibacterial mask and preparation method thereof |
| CN111960719A (en) * | 2020-08-11 | 2020-11-20 | 陕西宏基混凝土构件有限责任公司 | Lightweight aggregate concrete and preparation method thereof |
| CN113712046A (en) * | 2021-05-26 | 2021-11-30 | 北京崇高纳米科技有限公司 | Organic-inorganic compound for long-acting protection of microorganisms and preparation method thereof |
| CN113712046B (en) * | 2021-05-26 | 2023-10-24 | 北京崇高纳米科技有限公司 | Organic-inorganic compound capable of protecting microorganisms for long time and preparation method thereof |
| CN113615711A (en) * | 2021-06-19 | 2021-11-09 | 武汉京创崇高生物技术有限公司 | Long-acting microorganism protection composition and preparation method thereof |
| CN113999728A (en) * | 2021-10-13 | 2022-02-01 | 江苏今日卫生用品有限公司 | Efficient sterilization laundry detergent and preparation method thereof |
| CN115381854A (en) * | 2022-07-07 | 2022-11-25 | 广东省科学院生物与医学工程研究所 | Injectable antibacterial composite material and preparation method and application thereof |
| CN115381854B (en) * | 2022-07-07 | 2024-02-20 | 广东省科学院生物与医学工程研究所 | Injectable antibacterial composite material and preparation method and application thereof |
| CN115109665A (en) * | 2022-07-29 | 2022-09-27 | 成都汉德尔新材料有限公司 | Safe and environment-friendly disinfection and sterilization laundry detergent and preparation method thereof |
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