CN106857658B

CN106857658B - It is a kind of carry with, the Nano Silver table-ware disinfection liquid of efficient quick sterilization

Info

Publication number: CN106857658B
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: 2017-12-29
Anticipated expiration: 2037-03-30
Also published as: CN106857658A

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, miscellaneous disposable tableware gradually increases simultaneously.《Defend public place Students management regulations》It is to create good public places sanitary condition, prevention disease, the regulations for ensureing health and formulating.

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 inserts sterilization 2-5 minutes in boiling water；Moise-heat sterilization, the tableware for washing clean is inserted in steam box or case, is raised to temperature At 100 DEG C, 5-10 minutes are sterilized；Baking box sterilizes, such as infrared disinfection cabinet, and temperature is typically at 120 DEG C or so, 15-20 points of sterilization 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, much bacterium Ke Yi Nai Genggao temperature, the processing to these bacteriums are 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 polluting environment, developing immunity to drugs.Particularly antibioticses bactericide, its Liquid Residue generally require Extra post-processing, 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 conventional nano-Ag particles are easily reunited, while Nano Silver easily aoxidizes, and Nano Silver is for the shadow of the mankind Sound is not yet clear and definite, therefore the content of Nano Silver needs to control in certain scope, avoids causing the mankind imponderable shadow Ring；But when the content of Nano Silver reduces, its sterilizing performance needs to reappraise again, may be unable to reach complete 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 there is taste Moisten human skin, the advantages that reducing the 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, press 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：

As one embodiment of the present invention, the stabilizer is sodium pyrophosphate, pyridine dicarboxyl sodium, hydroxy-methylbenzene fork two Phosphoric acid, tartaric acid, sorbic acid, phytic acid, one or more of mixtures of potassium pyrophosphate.

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

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

As one embodiment of the present invention, the nano-ag composite is Nano silver piece, water-based chitosan and Yin Na The compound of rice corpuscles.

As one embodiment of the present invention, the parts by weight of the Nano silver piece, water-based chitosan and Nano silver grain Than for 1：(10-50)：(20-80).

As one embodiment of the present invention, the parts by weight of the Nano silver piece, water-based chitosan and Nano silver grain Than for 1：30：50.

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 parts by weight meter, nano-ag composite, surfactant, stabilizer, care agent and deionized water are mixed Stirring 2-4 hours are closed, are warming up to 30-50 DEG C, and maintain 3-4h, are cooled down, filtering, 2-3 hours is stood, produces.

Beneficial effect：

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

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

3rd, Nano Silver table-ware disinfection liquid provided by the invention, which has, moistens human skin, reduces the infringement to skin.

Brief description of the drawings

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

Embodiment

Participate in the election of the detailed description of the invention below for being preferable to carry out method 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 contradiction be present, the definition in this specification is defined.

As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " 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, but can include not expressly listed other key elements or Such a 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 of those descriptions, but relative normal Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme, It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.

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 limits, this, which is appreciated that, 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 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 plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " 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, and it is specific to represent that the present invention is not limited to this Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.

In addition, indefinite article " one kind " before key element of the present invention or component and "one" 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 by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".

" EVA " means the polymer prepared by polymerizeing at least two different monomers.Generic term " EVA " includes (its is general with term " terpolymer " for term " copolymer " (its typically to refer to the polymer prepared by two kinds of different monomers) To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization for planting monomer by polymerization four or more to manufacture Thing." blend " means that two or more polymer mixes the polymerization to be formed by physics or chemical method jointly Thing.

Nano-ag composite

Heretofore described nano-ag composite is the compound of Nano silver piece, water-based chitosan and Nano silver grain, is made Standby mode prepares Nano silver piece, the composite water soluble chitosan particle on Nano silver piece；Then Nano silver piece and water-based shell are gathered The compound of sugared particulate carries out mineral acid treatment, then to the compound of the Nano silver piece after processing and water-based chitosan particle and Nano silver grain it is compound, nano-ag composite is finally prepared.

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 After vinylpyrrolidone (mean molecule quantity 33000) is added to 50 milliliters of above-mentioned in the mixed solvent ultrasonic dissolutions, 6 millis are added 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 that 50 milliliters of above-mentioned in the mixed solvents are uniformly dissolved, it is standby.

Solution A and solution B is 1: 1 well mixed and be transferred in reaction vessel by volume, it is heated to and seethes with excitement back Flow and kept for 3 hours, then stop heating.After reaction stops, with water and ethanol, each 100 milliliters are cleaned and 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.

Water-based chitosan particle

The preparation method of heretofore described water-based chitosan particle is as follows：

1st, the preparation of carboxymethyl chitosan：

(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g NaOH solids, 100mL water, stirring swelling 1h, 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 being added dropwise.

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

(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, 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.It is freeze-dried and produces carboxymethyl chitosan.

2nd, the preparation of water-based chitosan particle：

(1) carboxymethyl chitosan sample is dissolved in distilled water, it is molten obtains the carboxymethyl chitosan that concentration is 0.5mg/mL 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 Stir 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.

(3) gained emulsion 20000rpm is centrifuged, removes supernatant, added distilled water and precipitation is blown to outstanding, freeze-drying.

Nano silver grain

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

1g dodecyl acid silver is dissolved in 20mL solvent toluenes, to abundant dissolving；Secondly, 6g lauryl amines are taken to be dissolved in In 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；Then, by the 1g acyl of decanedioic acid two Hydrazine is added in 20mL toluene, is stirred well to abundant 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 prepared is added drop-wise to the mixed of above-mentioned configuration dodecyl acid silver and lauryl amine Close in solution.Stop after reacting 60 minutes at normal temperatures, obtain the colloid of monodispersed Nano silver grain, be prepared above-mentioned The colloid of monodispersed Nano silver grain carry out centrifugation, sediment using acetone and butanol mixed solvent (volume ratio For 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 water-based chitosan particle

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

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

2nd, the Nano silver piece after ultrasound in step 1 and carboxymethyl chitosan sample dispersion 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, added distilled water and precipitation is blown to outstanding, freeze-drying, you can Obtain the compound crude product of Nano silver piece and water-based chitosan particle.

(4) Nano silver piece and the compound crude product of water-based chitosan particle obtained step (3) is dispersed in distilled water, 3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, then adds Na₂SO₃Terminating reaction, 89% ethanol solution is added, Stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce 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 being prepared Property chitosan particle the silver-colored common distribution of compound and dodecyl acid in toluene solvant；Secondly, lauryl amine is taken to be dissolved in first In benzene, stir to being completely dissolved, in the solution for the compound for being added to the silver-colored and water-based chitosan particle of above-mentioned dodecyl acid；So Afterwards, sebacic dihydrazide is added in toluene, is stirred well to abundant dissolving.Under stirring in normal temperature and simultaneously, it will prepare The solution constant current of sebacic dihydrazide be added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and water-based chitosan particle In the mixed solution of compound and lauryl amine.After reacting a period of time at normal temperatures, the colloid of nano-ag composite is obtained, will be upper State the colloid being prepared and carry out centrifugation, sediment utilizes the mixed solvent (volume ratio 2 of acetone and butanol：1) clean At least 3 times.Then, in 50 DEG C of drying, nano-ag composite is obtained.

Surfactant

Surfactant, refer to add the material that can make the interface state of its solution system that significant change occur on a small quantity.Tool There is fixed hydrophilic lipophilic group, aligned in the surface energy of solution.The molecular structure of surfactant has amphipathic：One It is hydrophobic grouping to hold as hydrophilic radical, the other end；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. can also be used as polar hydrophilic group；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 advantages of cationic surface active agent, is that cationic surface active agent has for all kinds plant Affinity, there is 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 at smooth and soft aspect better than other 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, the polyoxyethylene moon 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 parts by weight of the surfactant are 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

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

As a kind of preferred embodiment of the present invention, the stabilizer is tartaric acid.

Care agent

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

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, the wooden fruit of breast and cocoa butter.

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.

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 the thimerosal using Nano Silver as main sterilizing composition, original that Nano Silver can work Because one is that nano-Ag particles have superpower permeability, it can penetrate into bacterium, and then the physiology for further influenceing 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 either water produce superoxide radical or Hydroxyl radical free radical, this two classes material have extremely strong chemical property, can destroy the multiplication capacity of biological cell, suppress or kill Go out bacterium.But this requires that Nano Silver has several characteristics, first, 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 with penetration cell wall inside bacterium, but existing nano silver particles can be rolled into a ball It is poly-；Second, silver ion be by Nano Silver dissociate Lai, therefore in solution silver ion concentration be well below actual Nano Silver 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, water-based chitosan particle and silver nano-grain solve above-mentioned Railway Project simultaneously.Nano silver piece is due to depositing with sheet form Its phenomenon reunited can be far smaller than the situation of silver nano-grain, while it exists in the form of nanometer sheet so that it is in list The speed that hydroxyl radical free radical or superoxide radical are produced in the time of position is significantly larger than the nano-Ag particles after reuniting；Secondly it is water-based Chitosan with Nano silver piece it is compound after, after peroxide degradation, there is hole in its surface so that later stage Nano silver grain It can be dispersed in the hole on water-based chitosan surface, effectively prevent the reunion of Nano silver grain, while improve silver ion Dissociation.After water-based chitosan particle and Nano silver piece are compound simultaneously, the Nano Silver table-ware disinfection liquid retention cycle length, product Stability improves, and in the case of very small amount thimerosal, can effectively kill bacterium, reduces use cost and Liquid Residue, protects Retaining ring border.

Embodiment 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：

Embodiment 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：

Embodiment 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 One or more of mixtures of potassium phosphate.

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

Embodiment 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.

Embodiment 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, water-based chitosan and Nano silver grain.

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

Embodiment 8：Can carry at any time as described in embodiment 6, the Nano Silver table-ware disinfection liquid of efficient quick sterilization, The weight part ratio of the Nano silver piece, water-based chitosan and Nano silver grain is 1：30：50.

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

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

The present invention is specifically described below by embodiment.It is necessarily pointed out 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 the nonessential modifications and adaptations made according to the content of the invention described above, 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 in 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 33000) is weighed again is added to 50 milliliters of above-mentioned in the mixed solvent ultrasonic dissolutions 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 The silver-colored mixed solution of acid：Weigh 1 gram of silver nitrate and be added to the solution B that 50 milliliters of above-mentioned in the mixed solvents are uniformly dissolved, it is standby.

2nd, the compound of Nano silver piece and water-based chitosan particle：

1st, the preparation of carboxymethyl chitosan：

2nd, the compound of Nano silver piece and water-based chitosan particle：

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

(2) Nano silver piece after ultrasound in step (1) and carboxymethyl chitosan sample dispersion 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 obtains Nano silver piece and water-based chitosan particle Compound.

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

(5) Nano silver piece and the compound crude product of water-based chitosan particle obtained step (4) is dispersed in distilled water, 3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, then adds Na₂SO₃Terminating reaction, 89% ethanol solution is added, Stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce product.

3rd, nano-ag composite

The compound of the above-mentioned Nano silver piece being prepared and water-based chitosan particle and 1g dodecyls acid silver is common It is dispersed in 20mL toluene solvants；Secondly, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added to In the solution for stating the compound of dodecyl acid silver, Nano silver piece and water-based chitosan particle；Then, by 1g sebacic dihydrazides It is added in 20mL toluene, is stirred well to abundant 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 prepared is added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and water-based In the compound of chitosan particle and the mixed solution of lauryl amine.After reacting 60min at normal temperatures, nano-ag composite is obtained Colloid, the above-mentioned colloid that is prepared is subjected to centrifugation, (volume ratio is sediment using the mixed solvent of acetone and butanol 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, water-based chitosan 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 are scientific and technological from the huge victory in Hubei Co., Ltd, the polyoxyethylene myristyl ether are 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 of efficient quick sterilization meal Have thimerosal preparation technology, comprise the following steps for：

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

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

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

Embodiment 3：The present embodiment and the difference of embodiment 1 are that the nano-ag composite is silver nano-grain, described The preparation method of Nano silver grain is as follows：1g dodecyl acid silver is dissolved in 20mL solvent toluenes, to abundant dissolving；Its It is secondary, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；So Afterwards, 1g sebacic dihydrazide is added in 20mL toluene, is stirred well to abundant 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 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 being prepared is subjected to centrifugation, sediment using acetone with Mixed solvent (the volume ratio 2 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 and the difference of embodiment 1 are that the silver nano-grain is directly loaded in Nano silver piece On, the preparation method of the Nano silver piece is as follows with embodiment 1, the preparation method of the silver nano-grain load Nano silver piece：

By the above-mentioned Nano silver piece being prepared and the silver-colored common distribution of 1g dodecyls acid in 20mL toluene solvants；Its It is secondary, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be 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 abundant 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 prepared is added drop-wise to above-mentioned match somebody with somebody In the mixed solution for putting dodecyl acid silver, Nano silver piece and lauryl amine.After reacting 60min at normal temperatures, colloid is obtained, will be upper State the colloid being prepared and carry out centrifugation, sediment utilizes the mixed solvent (volume ratio 2 of acetone and butanol：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 and the difference of embodiment 1 are that the nano-ag composite is Argent grain and water-based shell The compound of glycan, specific preparation process is as follows,

1st, the preparation of carboxymethyl chitosan：

2nd, the preparation of water-based chitosan particle：

(3) by gained emulsion 20000rpm centrifuge, remove supernatant, add distilled water precipitation is blown it is outstanding, freeze-drying, obtain Water-based chitosan particle crude product；

(4) water-based chitosan particle crude product is dispersed in distilled water, adds 3% hydrogen peroxide, lucifuge stirring 0.1-0.5 Hour, then add Na₂SO₃Terminating reaction, 89% ethanol solution is added, stirred 0.5 hour at room temperature, centrifuged 20min, go Except supernatant, it is repeated 3 times, 50 DEG C of vacuum drying, produces water-based chitosan particle.

3rd, the compound of Argent grain and water-based chitosan：

Water-based chitosan particle and 1g dodecyl acid silver are dissolved in 20mL solvent toluenes, to abundant dissolving；Secondly, Take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；Then, 1g sebacic dihydrazide is added in 20mL toluene, is stirred well to abundant dissolving.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 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, the colloid of the above-mentioned monodispersed Nano silver grain being prepared is subjected to centrifugation, sediment utilizes acetone and fourth Mixed solvent (the volume ratio 2 of alcohol：1) clean at least 3 times.Then, in 50 DEG C of drying, Argent grain and water-based chitosan are obtained Compound.

The weight part ratio of the water-based chitosan and Nano silver grain is 30：50.

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

1st, the preparation of carboxymethyl chitosan：

2nd, the preparation of water-based chitosan particle：

(3) by gained emulsion 20000rpm centrifuge, remove supernatant, add distilled water precipitation is blown it is outstanding, freeze-drying, obtain Water-based chitosan particle.

3rd, the compound of Argent grain and water-based chitosan：

Embodiment 7：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is Nano silver piece and water-based The compound of chitosan, its preparation process is the same as the compound of Nano silver piece and water-based chitosan particle in embodiment 1.

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

2nd, the compound of Nano silver piece and water-based chitosan particle：

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

Embodiment 9：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is but described with embodiment 1 The compound of Nano silver piece and water-based chitosan particle is handled without peroxide degradation in nano-ag composite, and without following Step process：" Nano silver piece and the compound crude product of water-based chitosan particle that (5) obtain step (4) are dispersed in distilled water In, 3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, then adds Na₂SO₃Terminating reaction, it is molten to add 89% ethanol Liquid, stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce product.”

Embodiment 10：The present embodiment and the difference of embodiment 1 be, the Nano silver grain based on { 111 } crystal face, Its preparation method is as follows：By 90mg silver nitrates, 110mg PVP, 20mL ethylene glycol and 0.05mg NaCl are placed in 50mL polytetrafluoros In ethylene reaction container, dissolving is sufficiently stirred.It is placed in micro-wave oven and heating response is carried out 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 and the difference of embodiment 1 be, the Nano silver piece, water-based chitosan and silver nanoparticle The weight part ratio of particle is 1：5：10.

Performance test：

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

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, add distilled water to stir to 1000mL, 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, adjusts pH to 7.2-7.4, is heated molten Solution, is dispensed 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, filter paper that is sterile and drying 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 dried in incubator (37 DEG C) it is rear standby.

(2) preparation of print is compareed

Sterile 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

Concentration is dipped as 5 × 10 with sterile cotton swab⁵Cfu/mL~5 × 10⁶Cfu/mL tests bacteria suspension, in nutrient agar Uniformly smear 3 times on culture medium flat plate surface.Often smear 1 time, flat board should rotate 60 °, finally smear cotton swab around plate edge One week.Plate is covered, puts drying at room temperature 5min.

(4) bacteriostatic agent print is placed with

Feared subsample piece with sterile and be placed with planar surface.At a distance of more than 25mm between each print center, the week with flat board 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 cultivating 24h.With the diameter and record of vernier caliper measurement antibacterial ring size.

Experiment is repeated 3 times.The diameter of the diametrically-sample of antibacterial ring size=outside.Measure antibacterial ring size when, should select uniformly and entirely without The antibacterial ring size of bacteria growing is carried out.Measuring its diameter should be using 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 no bacteriostasis.

2nd, MIC experimentations

(1) sterilize：The glass apparatus (beaker, glass bar, pipette and culture dish) that will be used in antiseptic and experiment It is placed on progress high-temperature sterilization processing in digital display Constant Temp. Oven.

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

(3) then the antimicrobial for weighing 2mL with pipette is resisted in beaker with the PBS for weighing 38mL Microbial inoculum is diluted, and is stirred, 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, obtain 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 is taken out, photographs to record experiment clump count.

3rd, scourability

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

Secondary washing will be carried out by used Liquid Residue for the first time simultaneously, check detergency and bacteriostasis property.

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

Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment 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 will not formed due to the inaccuracy of language performance 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 covers.

Claims

1. it is 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：

The stabilizer is sodium pyrophosphate, pyridine dicarboxyl sodium, hydroxy-methylbenzene fork diphosphonic acid, tartaric acid, sorbic acid, the phosphorus of inositol six Acid, one or more of mixtures of potassium pyrophosphate；

The nano-ag composite is the compound of Nano silver piece, water-based chitosan and Nano silver grain；The Nano silver piece, water Property chitosan and Nano silver grain weight part ratio be 1：30：50；The Nano silver grain is based on { 200 } crystal face；It is described The particle diameter of nano-silver powder is 9.0 ± 3.1nm；

The water-based chitosan is carboxymethyl chitosan nano particle.

2. 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 NMF, opacifier and one kind in numb agent or to a variety of.

3. 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.

4. a kind of prepare can carry at any time described in claim any one of 1-3, 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 parts by weight meter, by nano-ag composite, surfactant, stabilizer, care agent and deionized water, mixing is stirred 2-4 hours are mixed, are warming up to 30-50 DEG C, and maintain 3-4h, are cooled down, filtering, 2-3 hours is stood, produces.