CN106857658A

CN106857658A - It is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization

Info

Publication number: CN106857658A
Application number: CN201710200934.3A
Authority: CN
Inventors: 沈平凡
Original assignee: Anhui Silver Lithium Biotechnology Development Co Ltd
Current assignee: Anhui Silver Lithium Biotechnology Development Co Ltd
Priority date: 2017-03-30
Filing date: 2017-03-30
Publication date: 2017-06-20
Anticipated expiration: 2037-03-30
Also published as: CN106857658B

Abstract

The present invention provide it is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, its preparing raw material, in parts by mass, comprising：0.1 0.5 parts of nano-ag composite；5 10 parts of surfactant；1000 parts of deionized water；1 10 parts of stabilizer；1 20 parts of care agent.

Description

It is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization

Technical field

The present invention relates to a kind of table-ware disinfection liquid, more particularly to a kind of table-ware disinfection liquid containing Nano Silver and its preparation Technique.

Technical background

With gradually stepping up for living standard, the mankind increasingly tend to the public places such as dining room, restaurant met, Food and drink activity.In public places, in order to easy to use, disposable tableware miscellaneous gradually increases simultaneously.《Defend public place Students management regulations》It is the regulations formulated to create good public places sanitary condition, prevention disease, guarantee health.

Meanwhile, tableware serves thousands of personnel during use so that on bacterium on tableware is also thousands of Ten thousand, such as Escherichia coli, salmonella, gold-coloured staphylococci, typhoid bacillus and shigella dysenteriae etc..Therefore, it is used in tableware Afterwards, it is necessary to which sterilization processing is carried out to tableware.The mode of conventional tableware sterilization processing has scalding, will wash the meal of cleaning Tool is inserted in boiling water and sterilized 2-5 minutes；Moise-heat sterilization, will wash during clean tableware inserts steam box or case, be raised to temperature At 100 DEG C, sterilize 5-10 minutes；Baking box is sterilized, such as infrared disinfection cabinet, and typically at 120 DEG C or so, sterilization 15-20 divides temperature Clock；The explosion of the meeting heat such as chemical disinfection, the tableware of non-refractory, particularly beer tool, deformation etc., can be used bleaching powder, chlorine sub- The medicining liquid dippings such as bright, potassium permanganate；Dishwashing detergent is sterilized using dish-washing machine.

But in the method for some above-mentioned table-ware disinfections, conventional scalding, moise-heat sterilization or baking box sterilization etc., Although temperature can reach 100-120 DEG C or so, the temperature of many bacterium Ke Yi Nai Genggao, the treatment to these bacteriums is past Toward the more effective disinfection way of needs.Secondly, conventional bactericide is divided into inorganic fungicide, organosulfureous fungicide, organophosphorus insecticidal Microbial inoculum, organoarsenic fungicide, substituted beneze-group fungicides, azoles fungicide, antibioticses bactericide or composite bactericide etc..One A little bactericide, such as organosulfureous fungicide, substituted beneze-group fungicides, azoles fungicide, antibioticses bactericide etc. often have Biological metabolism rate is low, the shortcomings of pollute environment, develop immunity to drugs.Particularly antibioticses bactericide, its Liquid Residue is generally required Extra later stage treatment, while bacterium also easily produces the superbacteria of antibiotic-resistant.

The antimicrobial spectrum of silver ion is extremely wide, and it is to staphylococcus aureus, Pseudomonas aeruginosa, pseudomonad, gonococcus, hemolytic Streptococcus, ETEC, fungi etc. kill effect, while under anaerobic also can bacteria growing inhibiting.Meanwhile, Nano-Ag particles have superpower permeability, subcutaneous 2mm sterilizations can be rapidly permeated into, to common bacteria, stubborn bacteria, drug-resistant bacteria And the tissue infection of fungus-caused higher depth has good bactericidal action.

But the nano-Ag particles of routine are easily reunited, while Nano Silver is easily aoxidized, and Nano Silver is for the shadow of the mankind Ring not yet clearly, therefore the content of Nano Silver needs control in certain scope, it is to avoid the mankind are caused with imponderable shadow Ring；But when the content reduction of Nano Silver, its sterilizing performance needs to reappraise, and may be unable to reach complete again Sterilizing performance.For this case, the present invention provides a kind of Nano Silver table-ware disinfection liquid, and it is less than in content Still there is the performance of efficient quick sterilization under 0.0004ppm, and it is environmentally safe, on human body without influence, while having taste Profit human skin, the advantages of reduce infringement to skin, and can carry with, and used solution is reusable, Still there is excellent sterilizing performance.

The content of the invention

The present invention provide it is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, its preparing raw material presses Mass parts meter, comprising：

As one embodiment of the present invention, it is described carry with, the Nano Silver table-ware disinfection of efficient quick sterilization Liquid, its preparing raw material, in parts by mass, comprising：

Used as one embodiment of the present invention, the stabilizer is sodium pyrophosphate, pyridine dicarboxyl sodium, hydroxy-methylbenzene fork two The mixture of one or more of phosphoric acid, tartaric acid, sorbic acid, phytic acid, potassium pyrophosphate.

As one embodiment of the present invention, the care agent be one kind in NMF, opacifier and numb agent or To various.

As one embodiment of the present invention, the surfactant be selected from nonionic surfactant and/or sun from Sub- surfactant.

Used as one embodiment of the present invention, the nano-ag composite is Nano silver piece, aqueous shitosan and Yin Na The compound of rice corpuscles.

As one embodiment of the present invention, the weight portion of the Nano silver piece, aqueous shitosan and Nano silver grain Than being 1：(10-50)：(20-80).

As one embodiment of the present invention, the weight portion of the Nano silver piece, aqueous shitosan and Nano silver grain Than being 1：30：50.

Used as one embodiment of the present invention, the Nano silver grain is based on { 200 } crystal face.

It is a kind of prepare it is above-mentioned can carry at any time, the preparation technology of the Nano Silver table-ware disinfection liquid of efficient quick sterilization, its Be characterised by, comprise the following steps for：

According to the weight portion meter, nano-ag composite, surfactant, stabilizer, care agent and deionized water are mixed Stirring 2-4 hours is closed, 30-50 DEG C is warming up to, and maintains 3-4h, cooled down, filtering stands 2-3 hours, obtains final product.

Beneficial effect：

1st, the content of Nano Silver is extremely low in the Nano Silver table-ware disinfection liquid that the present invention is provided, in 0.0004ppm or so, will not Imponderable influence is caused on environment and the mankind；

2nd, the Nano Silver table-ware disinfection liquid that the present invention is provided has rapidly and efficiently sterilized performance, and easy cleaning, saves into This；

3rd, the Nano Silver table-ware disinfection liquid that the present invention is provided has moist human skin, reduces the infringement to skin.

Brief description of the drawings

Fig. 1：The X-ray diffraction spectrogram of Nano silver grain.

Specific embodiment

The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.

As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, and can be including not expressly listed other key elements or This kind of composition, step, method, product or the intrinsic key element of device.

Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to the material that those are described, but relative normal Except rule impurity.When phrase " Consists of " is appeared in be rather than immediately following after theme in the clause of claim main body, It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.

Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.

Singulative includes that plural number discusses object, unless the context clearly dictates otherwise.It is " optional " or " any It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific Quantity, also including the acceptable part without cause the amendment of the change of related basic function close to the quantity.Phase Answer, a numerical value is modified with " about ", " about " etc., mean the invention is not restricted to the exact numerical.In some examples, approximately Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.

Additionally, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.

" polymer " means the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term " polymer " includes term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".

" EVA " means the polymer prepared by least two different monomers that are polymerized.Generic term " EVA " includes (its is general with term " terpolymer " for term " copolymer " (it is typically used to refer to the polymer prepared by two kinds of different monomers) It is used to refer to the polymer prepared by three kinds of different monomers).Its polymerization for also being manufactured comprising monomer is planted by polymerization four or more Thing." blend " means the polymerization that two or more polymer is mixed and formed jointly by physics or chemistry method Thing.

Nano-ag composite

Heretofore described nano-ag composite is the compound of Nano silver piece, aqueous shitosan and Nano silver grain, system Standby mode prepares Nano silver piece, the composite water soluble chitosan particle on Nano silver piece；Then it is poly- to Nano silver piece and aqueous shell The compound of sugared particulate carries out mineral acid treatment, then to the compound of the Nano silver piece after treatment and aqueous chitosan particle and Being combined for Nano silver grain, finally prepares nano-ag composite.

Nano silver piece

The preparation process of heretofore described Nano silver piece is as follows：

It is standby with 100 milliliters of preparing ethylene glycol and dimethylformamide mixed solvent by 1: 1 volume ratio；1 gram is weighed again to gather Vinylpyrrolidone (mean molecule quantity is 33000) is added in 50 milliliters of above-mentioned mixed solvents after ultrasonic dissolution, adds 6 millis Gram KBr and 6 milligrams of copper chlorides, ultrasonic dissolution it is uniform solution A, it is standby；Mixed solvent is prepared again and silver nitrate mixing is molten Liquid：Weigh 1 gram of silver nitrate and be added to the solution B being uniformly dissolved in 50 milliliters of above-mentioned mixed solvents, it is standby.

Solution A and solution B are well mixed and be transferred to reaction vessel at 1: 1 by volume, is heated to and is seethed with excitement back Flow and keep 3 hours, then stop heating.After reaction stops, with water and ethanol, each 100 milliliters are cleaned and are centrifuged, finally by institute The Nano silver piece for being dried and can obtain that the dry powder-shaped length of side is 40 nanometers, thickness is 10~15 nanometers must be precipitated.

Aqueous chitosan particle

The preparation method of heretofore described aqueous chitosan particle is as follows：

1st, the preparation of carboxymethyl chitosan：

(1) 10g shitosans (160kDa DD 79.01%) are weighed in 500mL beakers, 80mL isopropanols, 13.5g is added NaOH solids, 100mL water stirs swelling 1h, and reaction temperature is 50 DEG C.

(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after completion of dropping.

(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, plus Enter 70% ethanol solution except desalting, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each 2h long, freeze-drying obtains carboxymethyl chitosan crude product.

(4) by prepared carboxymethyl chitosan (1g), it is put into the ethanol of 100mL 80%, concentrated hydrochloric acid 5mL is added, at 60 DEG C Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95% Ethanol dehydration 3 times, each duration 2h.Freeze-drying obtains final product carboxymethyl chitosan.

2nd, the preparation of aqueous chitosan particle：

(1) carboxymethyl chitosan sample is dissolved in distilled water, obtains the carboxymethyl chitosan that concentration is 0.5mg/mL molten Liquid.

(2) CaCl that 2mL concentration is 1.0mg/mL is taken₂Solution is added in the above-mentioned carboxymethyl chitosan solutions of 5mL, room temperature Stirring 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.

(3) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying.

Nano silver grain

The preparation method of heretofore described Nano silver grain is as follows：

1g dodecyls acid silver is dissolved in 20mL solvent toluenes, to fully dissolving；Secondly, 6g lauryl amines are taken and is dissolved in In 30mL toluene, stir to being completely dissolved, be added in above-mentioned dodecyl acid silver solution；Then, by the acyl of decanedioic acid two of 1g Hydrazine is added in 20mL toluene, is stirred well to fully dissolving.The amount of final solvent toluene is controlled in 70mL.In normal temperature and simultaneously Under stirring, the solution constant current of the sebacic dihydrazide that will be prepared is added drop-wise to the mixed of the sour silver-colored and lauryl amine of above-mentioned configuration dodecyl In conjunction solution.Stop after reacting 60 minutes at normal temperatures, obtain the colloid of monodispersed Nano silver grain, prepared above-mentioned The colloid of monodispersed Nano silver grain carry out centrifugation, sediment using acetone and butanol mixed solvent (volume ratio It is 2：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-silver powder is obtained.The particle diameter of the nano-silver powder be 9.0 ± 3.1nm。

In the present invention, the Nano silver grain is based on { 200 } crystal face.

The compound of Nano silver piece and aqueous chitosan particle

The preparation method of the compound of heretofore described Nano silver piece and aqueous chitosan particle is as follows：

1st, by the above-mentioned Nano silver piece for preparing be dispersed in ethanol it is easy in, ultrasound is quiet after 1-3 hours under the ultrasound Put, take out；

2nd, the Nano silver piece and carboxymethyl chitosan sample dispersion after ultrasound in step 1 are obtained into carboxylic first in distilled water Base enclosure glycan and Nano silver piece mixed solution.

(2) CaCl is taken₂Solution is added in above-mentioned carboxymethyl chitosan and Nano silver piece mixed solution, is stirred at room temperature 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.

(3) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying, you can Obtain the compound crude product of Nano silver piece and aqueous chitosan particle.

(4) Nano silver piece and the compound crude product of aqueous chitosan particle for obtaining step (3) are dispersed in distilled water, 3% hydrogen peroxide is added, lucifuge is stirred 0.1-0.5 hours, is subsequently adding Na₂SO₃Terminating reaction, adds 89% ethanol solution, Stir 0.5 hour at room temperature, 20min is centrifuged, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying obtain final product product.

Nano-ag composite

In the present invention, the preparation method of the nano-ag composite is as follows：By the above-mentioned Nano silver piece and water for preparing Property chitosan particle compound and dodecyl acid silver common distribution in toluene solvant；Secondly, take lauryl amine and be dissolved in first In benzene, stir to being completely dissolved, be added in the solution of the compound of the silver-colored and aqueous chitosan particle of above-mentioned dodecyl acid；So Afterwards, sebacic dihydrazide is added in toluene, is stirred well to fully dissolving.Under stirring in normal temperature and simultaneously, will prepare The solution constant current of sebacic dihydrazide be added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and aqueous chitosan particle In the mixed solution of compound and lauryl amine.After a period of time of reaction at normal temperatures, the colloid of nano-ag composite is obtained, will be upper Stating the colloid for preparing carries out centrifugation, and using the mixed solvent of acetone and butanol, (volume ratio is 2 to sediment：1) clean At least 3 times.Then, in 50 DEG C of drying, nano-ag composite is obtained.

Surfactant

Surfactant, refers to add the interface state that can make its solution system on a small quantity that the material of significant change occurs.Tool There is fixed hydrophilic lipophilic group, can be aligned on the surface of solution.The molecular structure of surfactant has amphipathic：One It is hydrophilic radical to hold, and the other end is hydrophobic grouping；Hydrophilic radical is often polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amine Base and its salt, hydroxyl, amide groups, ehter bond etc. also can be used as polar hydrophilic groups；And hydrophobic grouping is often nonpolar hydrocarbon chain, such as 8 Individual carbon atom above hydrocarbon chain.

In the present invention, the surfactant is selected from nonionic surfactant and/or cationic surfactant.

Conventional cationic surfactant has amine salt cationic surfactant and quaternary ammonium salt cationic surface to live Property agent；

Suitable cationic surfactant includes：Alkyl trimethyl ammonium sodium, dialkyl dimethyl ammonium sodium and alkyl two Methyl-benzyl ammonium sodium.Quaternary ammonium salt cationic surfactant have low-corrosiveness and gentle smell and to heat, pH and have Machine thing has high stability.

The advantage of cationic surface active agent is that cationic surface active agent has for all kinds plant Affinity, with low-down toxicity, or even wherein using in the case of very small amount of cationic surface active agent It is very effective, and is tasteless and odorless.In addition, cationic surface active agent is better than other at smooth and soft aspect Surfactant.

Conventional nonionic surface active agent：Polyethylene glycol type nonionic surfactant, polyol type nonionic table Face activating agent；

Suitable nonionic surface active agent include polyoxyethylene ether, polyoxyethylene propylidene alkyl ether, Polyoxyethylene phenyl ether and polyoxyethylene fatty acid ester.Particularly with for stability be preferably polyoxyethylene Alkyl ether, polyoxyethylene propylidene alkyl ether and polyoxyethylene phenyl ether.Suitable example includes polyoxyethylene Octyl Ether, polyoxyethylene nonyl ethers, polyoxyethylene certain herbaceous plants with big flowers base ether, polyoxyethylene propylidene certain herbaceous plants with big flowers base ether, polyoxyethylene month Osmanthus base ether, polyoxyethylene propylidene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene propylidene tridecyl Ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl group Phenyl ether, polyoxyethylene nonylplenyl ether and polyoxyethylene styrenated phenyl ether.

In one embodiment of the invention, the surfactant is selected from alkyl trimethyl ammonium sodium, dialkyl group diformazan Base ammonium sodium, polyoxyethylene ether, polyoxyethylene nonyl ethers, polyoxyethylene myristyl ether, polyoxyethylene are stearic One or more in base ether.

In the present invention, the weight portion of the surfactant is 5-10 parts, more preferably 8 parts.

Deionized water

In the present invention, the deionized water is redistilled water, is bought from Shanghai joint-trial chemical reagent Co., Ltd.

Stabilizer

Used as a kind of preferred embodiment of the invention, the stabilizer is tartaric acid and/or sorbic acid.

Used as a kind of preferred embodiment of the invention, the stabilizer is tartaric acid.

Care agent

In the present invention, the care agent is one kind in NMF, opacifier and numb agent or to various.

Used as one embodiment of the present invention, the NMF is selected from glycerine, sorbierite, propane diols, Laneth-5 extremely 100th, lanolin alcohol, D-pantothenyl aleohol, polyethylene glycol (PEG) 200-10,000, macrogol ester, acyl lactylates, polyquaternium -7, Glyceryl cocounut oil acid esters/laurate, PEG-7 glyceryls cocounut oil acid esters, stearic acid, hydrolysis SP, silk-fibroin, Guar hydroxypropyl One or more in trimethyl ammonium chloride, alkyl polyglucosides/glycerol monolaurate, breast wood fruit and cocoa butter.

Used as one embodiment of the present invention, it is misery that the opacifier is selected from titanium dioxide, zinc oxide, methoxycinnamate One or more in ester, 4 methyl benzylidene camphor, Avobenzone, oxybenzone and Homosalate.

Used as one embodiment of the present invention, the numb agent is selected from asparagus juice, calamine, peppermint, menthol, camphor tree One or more in brain, antihistamine, steroids, benzocainum.

As one embodiment of the present invention, it is described carry with, the nanometer silverware of efficient quick sterilization disappears Venom, its preparing raw material, in parts by mass, comprising：

The second aspect of the present invention provide it is a kind of prepare it is described can carry at any time, the nanometer silverware of efficient quick sterilization The preparation technology of thimerosal, comprise the following steps for：

Mechanism is explained：In taking Nano Silver as the thimerosal of main sterilizing composition, the original that Nano Silver can work Because one is that nano-Ag particles have superpower permeability, can penetrate into bacterium, and then further the physiology of influence bacterium is lived Property；Reason two is that silver ion has electropositive, and bacterium surface has elecrtonegativity, between the two because positive and negative attraction, further shadow Ring the physiologically active of bacterium；Reason three be Nano Silver under the irradiation of light, can and air or water produce superoxide radical or Hydroxyl radical free radical, this two classes material has extremely strong chemical property, can destroy the multiplication capacity of biological cell, suppresses or kills Go out bacterium.But this requires that Nano Silver has several characteristics, one is that the particle diameter of Nano Silver can not be too big because particle diameter 25nm with Under nano silver particles can be just directly entered inside bacterium with penetration cell wall, but existing nano silver particles can be rolled into a ball It is poly-；Two is that silver ion is to be dissociated to come by Nano Silver, therefore the concentration of silver ion is well below actual Nano Silver in solution Concentration, this have impact on the sterilizing actual performance of silver ion.The present invention is by preparing nano-ag composite, i.e. silver nanoparticle Piece, aqueous chitosan particle and silver nano-grain solve above-mentioned Railway Project simultaneously.Nano silver piece is due to depositing with sheet form , its reunite phenomenon can be far smaller than silver nano-grain situation, while it exists in the form of nanometer sheet so that it is in list The speed of hydroxyl radical free radical or superoxide radical is produced to be significantly larger than the nano-Ag particles after reuniting in the time of position；Secondly it is aqueous After being combined with Nano silver piece, after peroxide degradation, there is hole to shitosan in its surface so that later stage Nano silver grain Can be dispersed in the hole on aqueous shitosan surface, effectively prevent the reunion of Nano silver grain, while improve silver ion Dissociation.After aqueous chitosan particle and Nano silver piece are compound simultaneously, the Nano Silver table-ware disinfection liquid retention cycle is long, product Stability is improved, and in the case of very small amount thimerosal, can effectively kill bacterium, reduces use cost and Liquid Residue, is protected Retaining ring border.

Implementation method 1：Present embodiment provide it is a kind of carry with, the Nano Silver table-ware disinfection of efficient quick sterilization Liquid, its preparing raw material, in parts by mass, comprising：

Implementation method 2：Carrying with as tdescribed in embodiment 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, Its preparing raw material, in parts by mass, comprising：

Implementation method 3：Carrying with as tdescribed in embodiment 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The stabilizer is sodium pyrophosphate, pyridine dicarboxyl sodium, hydroxy-methylbenzene fork diphosphonic acid, tartaric acid, sorbic acid, phytic acid, Jiao The mixture of one or more of potassium phosphate.

Implementation method 4：Carrying with as tdescribed in embodiment 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The care agent is one kind in NMF, opacifier and numb agent or to various.

Implementation method 5：Carrying with as tdescribed in embodiment 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The surfactant is selected from nonionic surfactant and/or cationic surfactant.

Implementation method 6：Carrying with as tdescribed in embodiment 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The nano-ag composite is the compound of Nano silver piece, aqueous shitosan and Nano silver grain.

Implementation method 7：Can carry at any time as described in implementation method 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The weight part ratio of the Nano silver piece, aqueous shitosan and Nano silver grain is 1：(10-50)：(20-80).

Implementation method 8：Can carry at any time as described in implementation method 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The weight part ratio of the Nano silver piece, aqueous shitosan and Nano silver grain is 1：30：50.

Implementation method 9：Can carry at any time as described in implementation method 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The Nano silver grain is based on { 200 } crystal face.

Implementation method 10：It is a kind of prepare described in implementation method any one of 1-9 can carry at any time, efficient quick sterilization is received Rice silverware thimerosal preparation technology, comprise the following steps for：

The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some nonessential modifications and adaptations that content according to the invention described above is made, still fall within protection scope of the present invention.

In addition, if without other explanations, raw materials used is all commercially available, and number used by following material is weight Part.

Embodiment 1：

The present embodiment provide it is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, its preparing raw material, In parts by mass, comprising：

Wherein, the preparation method of the nano-ag composite is as follows：

First, Nano silver piece：It is standby with 100 milliliters of preparing ethylene glycol and dimethylformamide mixed solvent by 1: 1 volume ratio； 1 gram of polyvinylpyrrolidone (mean molecule quantity is 33000) is weighed again is added to ultrasonic dissolution in 50 milliliters of above-mentioned mixed solvents Afterwards, add 6 milligrams of KBrs and 6 milligrams of copper chlorides, ultrasonic dissolution it is uniform solution A, it is standby；Mixed solvent and nitre are prepared again Sour silver mixed solution：Weigh 1 gram of silver nitrate and be added to the solution B being uniformly dissolved in 50 milliliters of above-mentioned mixed solvents, it is standby.

2nd, the compound of Nano silver piece and aqueous chitosan particle：

1st, the preparation of carboxymethyl chitosan：

2nd, the compound of Nano silver piece and aqueous chitosan particle：

(1) by the above-mentioned Nano silver piece for preparing be dispersed in ethanol it is easy in, ultrasound is quiet after 1-3 hours under the ultrasound Put, take out；

(2) Nano silver piece and carboxymethyl chitosan sample dispersion after ultrasound in step (1) are obtained into carboxylic in distilled water Methyl chitosan and Nano silver piece mixed solution, the wherein concentration of carboxymethyl chitosan are 0.5mg/mL.

(3) CaCl that 2mL concentration is 1.0mg/mL is taken₂Solution is added to the above-mentioned carboxymethyl chitosans of 5mL and Nano silver piece In mixed solution, 30min is stirred at room temperature.Solution is changed into milky emulsion, you can obtain Nano silver piece and aqueous chitosan particle Compound.

(4) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying, you can Obtain the compound crude product of Nano silver piece and aqueous chitosan particle.

(5) Nano silver piece and the compound crude product of aqueous chitosan particle for obtaining step (4) are dispersed in distilled water, 3% hydrogen peroxide is added, lucifuge is stirred 0.1-0.5 hours, is subsequently adding Na₂SO₃Terminating reaction, adds 89% ethanol solution, Stir 0.5 hour at room temperature, 20min is centrifuged, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying obtain final product product.

3rd, nano-ag composite

The compound of the above-mentioned Nano silver piece for preparing and aqueous chitosan particle and 1g dodecyls acid silver is common It is dispersed in 20mL toluene solvants；Secondly, 6g lauryl amines are taken and is dissolved in 30mL toluene, stirred to being completely dissolved, be added to In the solution of the compound for stating dodecyl acid silver, Nano silver piece and aqueous chitosan particle；Then, by 1g sebacic dihydrazides It is added in 20mL toluene, is stirred well to fully dissolving, the amount of final solvent toluene is in 70mL.Stir in normal temperature and simultaneously Under, the solution constant current of the sebacic dihydrazide that will be prepared is added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and aqueous In the compound of chitosan particle and the mixed solution of lauryl amine.At normal temperatures after reaction 60min, nano-ag composite is obtained Colloid, centrifugation is carried out by the above-mentioned colloid for preparing, and using the mixed solvent of acetone and butanol, (volume ratio is sediment 2：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-ag composite is obtained.

In the present embodiment, the Nano silver grain is based on { 200 } crystal face.

In the present embodiment, the weight part ratio of the Nano silver piece, aqueous shitosan and Nano silver grain is 1：30：50.

Surfactant：Surfactant described in the present embodiment is trimethyl ammonium iodide and polyoxyethylene Myristyl ether is 1 according to weight ratio：1 mixture, the trimethyl ammonium iodide purchase is scientific and technological from the huge victory in Hubei Co., Ltd, the polyoxyethylene myristyl ether is bought from Guangzhou Rui Yang surfactants Co., Ltd.

Deionized water is redistilled water, is bought from Shanghai joint-trial chemical reagent Co., Ltd.

Stabilizer is L-TARTARIC ACID, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.

NMF is glycerine, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.

Opacifier is titanium dioxide, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.

Numb agent is asparagus juice, is bought from Guangzhou Yu Tai Chemical Industry Science Co., Ltd.

The second aspect of the present embodiment provide it is a kind of prepare it is described can carry at any time, the Nano Silver meal of efficient quick sterilization Have thimerosal preparation technology, comprise the following steps for：

According to the weight portion meter, nano-ag composite, surfactant, stabilizer, care agent and deionized water are mixed Stirring 3 hours is closed, 50 DEG C are warming up to, and maintains 3h, cooled down, filtering stands 2 hours, obtains final product.

The content that the nano-ag composite is measured in thimerosal is approximately equal to 0.0004ppm.

Embodiment 2：The present embodiment is that the nano-ag composite is Nano silver piece, the silver with the difference of embodiment 1 The preparation method of nanometer sheet is with embodiment 1.

Embodiment 3：The present embodiment is that the nano-ag composite is silver nano-grain, described with the difference of embodiment 1 The preparation method of Nano silver grain is as follows：1g dodecyls acid silver is dissolved in 20mL solvent toluenes, to fully dissolving；Its It is secondary, take 6g lauryl amines and be dissolved in 30mL toluene, stir to being completely dissolved, it is added in above-mentioned dodecyl acid silver solution；So Afterwards, the sebacic dihydrazide of 1g is added in 20mL toluene, is stirred well to fully dissolving.Control the amount of final solvent toluene In 70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide that will be prepared is added drop-wise to above-mentioned configuration 12 In the mixed solution of alkyl acid silver and lauryl amine.Stop after reacting 60 minutes at normal temperatures, obtain monodispersed Nano silver grain Colloid, the colloid of the above-mentioned monodispersed Nano silver grain for preparing is carried out into centrifugation, sediment using acetone with (volume ratio is 2 to the mixed solvent of butanol：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-silver powder is obtained.The nanometer The particle diameter of silver powder is 9.0 ± 3.1nm.

Embodiment 4：The present embodiment is that the silver nano-grain is directly loaded in Nano silver piece with the difference of embodiment 1 On, the preparation method of the Nano silver piece is with embodiment 1, and the preparation method of the silver nano-grain load Nano silver piece is as follows：

By the above-mentioned Nano silver piece for preparing and 1g dodecyls acid silver common distribution in 20mL toluene solvants；Its It is secondary, take 6g lauryl amines and be dissolved in 30mL toluene, stir to being completely dissolved, it is added to above-mentioned dodecyl acid silver and Nano silver piece Solution in；Then, 1g sebacic dihydrazides are added in 20mL toluene, are stirred well to fully dissolving, final solvent first The amount of benzene is in 70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide that will be prepared is added drop-wise to above-mentioned matching somebody with somebody In putting dodecyl acid silver, the mixed solution of Nano silver piece and lauryl amine.At normal temperatures after reaction 60min, colloid is obtained, will be upper Stating the colloid for preparing carries out centrifugation, and using the mixed solvent of acetone and butanol, (volume ratio is 2 to sediment：1) clean At least 3 times.Then, in 50 DEG C of drying, silver nano-grain load Nano silver piece is obtained.

Embodiment 5：The present embodiment is that the nano-ag composite is Argent grain and aqueous shell with the difference of embodiment 1 The compound of glycan, specific preparation process is as follows,

1st, the preparation of carboxymethyl chitosan：

2nd, the preparation of aqueous chitosan particle：

(3) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying is obtained Aqueous chitosan particle crude product；

(4) aqueous chitosan particle crude product is dispersed in distilled water, adds 3% hydrogen peroxide, lucifuge stirring 0.1-0.5 Hour, it is subsequently adding Na₂SO₃Terminating reaction, adds 89% ethanol solution, stirs 0.5 hour at room temperature, and 20min is centrifuged, and goes Except supernatant, it is repeated 3 times, 50 DEG C of vacuum drying obtain final product aqueous chitosan particle.

3rd, the compound of Argent grain and aqueous shitosan：

Aqueous chitosan particle and 1g dodecyls acid silver are dissolved in 20mL solvent toluenes, to fully dissolving；Secondly, Take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in above-mentioned dodecyl acid silver solution；Then, The sebacic dihydrazide of 1g is added in 20mL toluene, fully dissolving is stirred well to.The amount of final solvent toluene is controlled to exist 70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide that will be prepared is added drop-wise to above-mentioned configuration dodecane In the mixed solution of base acid silver and lauryl amine.Stop after reacting 60 minutes at normal temperatures, obtain monodispersed Nano silver grain Colloid, centrifugation is carried out by the colloid of the above-mentioned monodispersed Nano silver grain for preparing, and sediment utilizes acetone and fourth (volume ratio is 2 to the mixed solvent of alcohol：1) clean at least 3 times.Then, in 50 DEG C of drying, Argent grain and aqueous shitosan are obtained Compound.

The weight part ratio of the aqueous shitosan and Nano silver grain is 30：50.

Embodiment 6：The present embodiment is that the nano-ag composite is Argent grain and aqueous shell with the difference of embodiment 1 The compound of glycan, specific preparation process is as follows,

1st, the preparation of carboxymethyl chitosan：

2nd, the preparation of aqueous chitosan particle：

(3) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying is obtained Aqueous chitosan particle.

3rd, the compound of Argent grain and aqueous shitosan：

The weight part ratio of the aqueous shitosan and Nano silver grain is 30：50.

Embodiment 7：The present embodiment is with the difference of embodiment 1, and the nano-ag composite is Nano silver piece and aqueous The compound of shitosan, its preparation process with Nano silver piece and aqueous chitosan particle in embodiment 1 compound.

Embodiment 8：The present embodiment is with the difference of embodiment 1, and the nano-ag composite is Nano silver piece and aqueous The compound of shitosan, its preparation process is as follows：1st, the preparation of carboxymethyl chitosan：

2nd, the compound of Nano silver piece and aqueous chitosan particle：

(4) gained emulsion 20000rpm is centrifuged, removes supernatant, add distilled water that precipitation is blown into outstanding, freeze-drying, you can Obtain the compound of Nano silver piece and aqueous chitosan particle.

Embodiment 9：The present embodiment is with the difference of embodiment 1, and the nano-ag composite is with embodiment 1 but described The compound of Nano silver piece and aqueous chitosan particle is processed without peroxide degradation in nano-ag composite, and without following Step process：" Nano silver piece and the compound crude product of aqueous chitosan particle that (5) obtain step (4) are dispersed in distilled water In, 3% hydrogen peroxide is added, lucifuge is stirred 0.1-0.5 hours, is subsequently adding Na₂SO₃Terminating reaction, adds 89% ethanol molten Liquid, stirs 0.5 hour at room temperature, and 20min is centrifuged, and removes supernatant, is repeated 3 times, 50 DEG C of vacuum drying, obtains final product product.”

Embodiment 10：The present embodiment is with the difference of embodiment 1, the Nano silver grain based on { 111 } crystal face, Its preparation method is as follows：By 90mg silver nitrates, the NaCl of 110mg PVP, 20mL ethylene glycol and 0.05mg is placed in 50mL polytetrafluoros In ethylene reaction container, dissolving is sufficiently stirred for.Be placed in micro-wave oven carried out heating response under 320W, in reaction 3 minutes Take out afterwards and obtain product, reacted product after natural cooling, is carried out clearly with acetone, ethanol and ultra-pure water successively at room temperature Wash：Cleaning agent, the dispersion product under ul-trasonic irradiation are added, then 20 minutes are centrifuged with precipitated nanocrystals solid with 4500rpm rotating speeds, Altogether in triplicate.After product cleaning, preserved after being disperseed with ultra-pure water.

Embodiment 11：The present embodiment is with the difference of embodiment 1, the Nano silver piece, aqueous shitosan and silver nanoparticle The weight part ratio of particle is 1：5：10.

Performance test：

1st, antibacterial ring size is determined：Anti-microbial property detection using staphylococcus aureus and Escherichia coli as gram-positive bacteria and The representative of Gram-negative bacteria, using the antibacterial around-France anti-microbial property to evaluate material.

The preparation of 1.1 culture mediums

The preparation of PBS：Disodium hydrogen phosphate 2.83g is weighed respectively, and phosphoric acid dioxy potassium L36g is placed in the big of 1000mL In sesame seed cake, plus distilled water is to 1000mL, stirs, and until completely dissolved, pH to 7.2-7.4 is adjusted with sodium hydroxide solution, in 121 DEG C of pressuresteam sterilization 20min are standby.

Escherichia coli, staphylococcus aureus solid medium (LB)：Tryptone 10g, beef extract 5g, NaCl 5g, fine jade Cosmetics 20g, distilled water 1000mL.Prepare：Mentioned component is taken, is added in 1000mL distilled water, adjust pH to 7.2-7.4, heated molten Solution, dispenses in rearmounted high-pressure steam sterilizing pan, and sterilize 30min in 121 DEG C.This medium component prepare be suitable for Escherichia coli and Staphylococcus aureus solid medium.

1.2 antibacterial ring sizes are tested

(1) preparation of bacteria inhibition tablet

To liquid bacteriostatic agent, aseptic and dry filter paper is taken.Every is added dropwise the antibacterial μ L of agent solution 20, afterwards by filter paper Lie against in the sterilized petri dishes of cleaning, put and dry in incubator (37 DEG C) rear standby.

(2) preparation of print is compareed

Aseptic dry filter paper piece is taken, the μ L of starch solution 20 are added dropwise, it is standby after drying.

(3) inoculation of test organisms

It is 5 × 10 to dip concentration with sterile cotton swab⁵Cfu/mL~5 × 10⁶Cfu/mL tests bacteria suspension, in nutrient agar Culture medium flat plate surface uniform application 3 times.Often smear 1 time, flat board should rotate 60 °, finally cotton swab is smeared around plate edge One week.Plate is covered, drying at room temperature 5min is put.

(4) bacteriostatic agent print is placed with

Feared subsample piece and be placed with planar surface with aseptic.At a distance of more than 25mm, the week with flat board between each print center Edge is at a distance of more than 15rmn.After being placed with, with the light pressure-like piece of aseptic nipper, it is set to be close to planar surface.Glass dish is covered, is put In 37 DEG C of insulating boxs, result is observed after culture 24h.With the diameter of vernier caliper measurement antibacterial ring size and record.

Experiment is repeated 3 times.The diameter of the diametrically-sample of antibacterial ring size=outward.During measurement antibacterial ring size, should select it is uniform and entirely without The antibacterial ring size of bacteria growing is carried out.Measuring its diameter should be with antibacterial ring size outer as boundary.Inhibition zone diameter is more than 7nim, has been judged to antibacterial Effect；Inhibition zone diameter is less than or equal to 7mm, is judged to without bacteriostasis.

2nd, MIC experimentations

(1) sterilize：The glass apparatus (beaker, glass bar, pipette and culture dish) that will be used in antiseptic and experiment Being placed in digital display Constant Temp. Oven carries out high-temperature sterilization treatment.

(2) bacterium solution prepares：The strain of preservation is inoculated on LB bases (staphylococcus aureus) with method of scoring with collarium is taken, 24h is cultivated in 37 DEG C of incubators, is taken during typical bacterium colony moves on to the conical flask equipped with culture medium, rocked under the conditions of 37 DEG C Culture 24h, a series of dilution is carried out by PBS to culture medium, makes bacteria suspension concentration 1 × 10⁷-2×10⁷μg/ ML, it is standby.

(3) antimicrobial of 2mL is weighed in beaker with pipette, then resisted with the PBS for weighing 38mL Microbial inoculum is diluted, and stirs, and forms the PBS dilutions that antimicrobial agent concentration is 5.0% (volume fraction).Take the sample of the concentration Product 10mL, then using double dilution method, obtains a series of sample of concentration：500,250,125,62.5,31.25 μ g/mL (ppm)。

(4) above-mentioned concentration sample and blank sample 1mL are taken, is mixed with 1mL bacteria suspensions, by each pipe bacterium transferred species LB flat board cultures On base, after being cultivated 24 hours at 37 DEG C, culture dish observation, Taking Pictures recording experiment clump count are taken out.

3rd, scourability

The detergency of this product is detected with reference to detergency detection method in GB 9985-2000 standards

Used Liquid Residue for the first time is carried out into secondary washing simultaneously, detergency and bacteriostasis property is checked.

4th, security test：With reference to the cytotoxicity experiments of GB/T 16886.5, the cytotoxicity of all embodiments is 0 Level.

The antibacterial ring size experimental results of table 1 and detergency test result

Embodiment	Antibacterial ring size is tested	Secondary antibacterial ring size experiment	Detergency test	Secondary washing power is tested
					Example 1	17.0	16.9	99.9%	99.8%
Example 2	8.5	7.3	70.3%	65.4%
					Example 3	9.0	7.5	76.1%	70.8%
Example 4	7.5	6.8	65.8%	60.2%
					Example 5	12.0	11.1	89.3%	83.8%
Example 6	10.8	9.8	82.1%	76.8%
					Example 7	11.8	10.5	86.1%	81.2%
Example 8	9.8	8.9	79.3%	74.4%
					Example 9	12.8	11.3	97.8%	93.1%
Example 10	12.5	10.8	95.2%	90.0%
					Example 11	14.1	12.9	98.5%	92.1%

The MIC test results of table 2

Note：" ++ " to represent and grown a large amount of bacteriums on culture medium, show that suppression (anti-) microbial inoculum does not press down (anti-) bacterium work to bacterium With；"+" represented on culture medium with the presence of a small amount of bacterium, shows that pressing down (anti-) microbial inoculum has certain suppression (anti-) bacterium effect to bacterium； " ± ", represents in culture medium there is few bacterium, shows that press down (anti-) microbial inoculum has larger suppression (anti-) bacterium to act on to bacterium；"-" is represented Without bacteria living in culture medium, show that suppression (anti-) microbial inoculum has complete suppression (anti-) bacterium to act on to bacterium.

Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment Combination selection implementation method explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim is covered.

Claims

1. a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that its preparing raw material, press Mass parts meter, comprising：

2. carrying with described in claim 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that its Preparing raw material, in parts by mass, comprising：

3. carrying with described in claim 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute It is sodium pyrophosphate, pyridine dicarboxyl sodium, hydroxy-methylbenzene fork diphosphonic acid, tartaric acid, sorbic acid, phytic acid, burnt phosphorus to state stabilizer The mixture of one or more of sour potassium.

4. carrying with described in claim 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute Care agent is stated for the one kind in NMF, opacifier and numb agent or to various.

5. carrying with described in claim 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute State surfactant and be selected from nonionic surfactant and/or cationic surfactant.

6. carrying with described in claim 1, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute State the compound that nano-ag composite is Nano silver piece, aqueous shitosan and Nano silver grain.

7. can carry at any time described in claim 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute The weight part ratio for stating Nano silver piece, aqueous shitosan and Nano silver grain is 1：(10-50)：(20-80).

8. can carry at any time described in claim 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute The weight part ratio for stating Nano silver piece, aqueous shitosan and Nano silver grain is 1：30：50.

9. can carry at any time described in claim 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, it is characterised in that institute Nano silver grain is stated based on { 200 } crystal face.

10. it is a kind of prepare described in claim any one of 1-9 can carry at any time, the Nano Silver table-ware disinfection of efficient quick sterilization The preparation technology of liquid, it is characterised in that comprise the following steps for：

According to the weight portion meter, by nano-ag composite, surfactant, stabilizer, care agent and deionized water, mixing is stirred Mix 2-4 hours, be warming up to 30-50 DEG C, and maintain 3-4h, cool down, filtering stands 2-3 hours, obtains final product.