CN102845471B - Silver-based composite particle, preparation method of the silver-based composite particle and antibacterial agent containing the silver-based composite particle - Google Patents
Silver-based composite particle, preparation method of the silver-based composite particle and antibacterial agent containing the silver-based composite particle Download PDFInfo
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Abstract
The invention discloses a silver-based composite particle having bactericidal effects and a preparation method of the silver-based composite particle, and especially relates to silica/silver composite powder which has a core-shell structure, contains silver element particles or a silver-based compound having a radial concentration gradient and has strong sterilization effects, and an antibacterial agent containing the silver element particle or silver-based compound composite particles as main ingredients. The antibacterial agent has washing resistance and photochromism resistance.
Description
Technical field
The present invention relates to a kind of money base composite granule with bactericidal action, particularly, relate to and a kind ofly there is nucleocapsid structure and wherein simple substance silver or money base compound have radially silica/argentum composite powder body of concentration gradient, it has strong bactericidal action, have simultaneously water-fastness, the resistance to feature such as photochromic.
Background technology
Simple substance silver or money base compound have very strong bactericidal action, and this is mainly because the outer list of silver element is easy to obtain and lose.Particularly, as a kind of inorganic metal anti-biotic material, silver-containing antibacterial agent has caused people's extensive concern.Particularly, owing to comparing with organic antibacterial agent, inorganic metal anti-biotic material have wide spectrum, efficient, have no side effect and the advantage such as be difficult for developing immunity to drugs, people are also more and more deep to its research.Yet because silver is very responsive to light, thereby cause its easy variable color, this is one of silver-colored major limitation as antibacterial agent application always.
At present the research of money base antibacterial agent is mainly concentrated on to the following aspects:
1) by ion exchange, silver ion is embedded and had in the carrier of ion exchange character, as zeolite, layered phosphates etc., for example CN1615700A1, in CN101092493A and CN1762218A, loads on mesoporous material, zeolite or nanometer SiO by ZnO or Ag
2on particle, prepare support type anti-biotic material;
2), by high temperature sintering, silver ion embeds in support crystal lattice, mainly with lattice defect form, exists, for example, in CN1771807A, described the inorganic antiseptic of silver-doped in ZnO lattice;
3) select to have with silver ion the ligand molecular of strong coordination ability, form stable silver complex solution, for example in CN1736204A, use sodium thiosulfate or sodium sulphite and silver chlorate or silver acetate to carry out complexing, make after silver complex again with Ludox and zinc compound together through mixing, the processing such as calcining, obtain anti-biotic material;
4) Nano Silver or silver-colored difficulty soluble salt or silver ion simple physical inorganic with other or natural or organic antibacterial agent is mixed;
5) dispersion liquid of silver nano-grain or at the area load nano-Ag particles of other carrier, for example, carry out composite mixing by nano-ZnO and nanometer Ag in CN1759682A, thereby obtain anti-biotic material.
In these prior aries, by high temperature treatment, make silver ion enter support crystal lattice and can to a certain degree improve its photostability, yet this will cause carrier granular sintering, agglomeration, dispersed variation.In addition, because particle is grown up, also make the adhesion of itself and fabric fibre decline.
By ion exchange, can make silver ion enter in the carrier with ion-exchange capacity, for example, zeolite, layered phosphates, clay etc.Can weaken to a certain extent photochromism like this.Yet, along with silver-colored load capacity increase photochromism is still very serious.In addition, it is also undesirable that the carrier material with ion-exchange performance often has larger particle size, dispersiveness, and the adhesion of fabric fibre is poor, not water-fastness.
By strong part and silver ion complexation, can improve the stability of silver ion, and can form true solution.Yet the greatest problem of this product is not water-fastness, in addition, some parts have toxicity.In order to reduce costs, reduce the consumption of silver ion, in inorganic antiseptic preparation process, often adopt silver and other inorganic antiseptic such as the composite method such as zinc, copper.In said method, Nano Silver and other inorganic antiseptic particles are random mixing just, silver or money base compound are randomly dispersed in particle surface, particle surface and inner silver or the distribution of money base compound do not have level, this makes other components can not be effectively to Nano Silver or money base compound, play the effect of shielded from light, therefore, be still difficult to avoid the photochromic of silver components wherein.
The drawback existing for above-mentioned prior art, people attempt the argentiferous microparticle antibacterial agent that preparation has nucleocapsid structure in recent years, and it roughly can be summarized as following two kinds of modes:
Method is to take non-silver components as a core, and silver nano-grain is shell, and this structure is mainly to play load and the fixedly effect of Nano Silver, but silver is not had to the effect of shielding light.
Another method is to take Nano Silver as core, other component as silica be shell, Chinese patent application 200710118942.X and 201010140269.1 for example.This structure is used to stop the reunion of silver nano-grain and controls silver-colored rate of release, yet, the complicated process of preparation of this nucleocapsid structure material, main is, silica is visible transparent, for Nano Silver that can responding to visible light, particularly for other compound of silver ion or silver, can not play the effect of shielding visible ray, and this improvement is mainly for granularity and the pattern of particle, and little to the light resistance of money base antibacterial agent and water-wash resistance effect.
Summary of the invention
The technical scheme of the present invention that the problem that the present inventor exists for above-mentioned prior art just proposes, in the present invention simple substance silver particles or silver compound and carrier are carried out to composite formation particle, and the concentration at granule interior silver exists gradient to distribute, thereby has effectively overcome the problems of the prior art.
One aspect of the present invention provides a kind of composite particles that comprises simple substance silver particles or silver compound, wherein simple substance silver particles or silver compound are carried on carrier, it is characterized in that the simple substance silver particles of described composite particles inside or the concentration of silver compound exist gradient to distribute.Wherein said carrier there is no particular restriction, it should be to be not more than the inorganic amorphous material that can keep undefined structure and form fine and close aggregate particle in thermal treatment at the temperature of 1200 ℃ at normal pressure, and physico chemical property are stable, can not react with silver-colored simple substance or silver compound.Particularly, can be preferably silica for being selected from one or more in silica, titanium phosphate, calcium phosphate, zeolite, diatomite and calcium carbonate, and be preferably white.
In described composite particles of the present invention, the carrier based on 100 weight portions, the amount of simple substance silver particles or silver compound is 0.1-10 weight portion, is preferably 0.5-5 weight portion, more preferably 0.6-4 weight portion, most preferably is 2 weight portions.When simple substance silver particles or silver compound amount are less than 0.1 weight portion, bactericidal effect is not obvious; When simple substance silver particles or silver compound amount are greater than 10 weight portion, cause final composite particles to reunite to increase, cost significantly improves.
Preferably, in described composite particles of the present invention, can further include can shielded from light material, described can shielded from light material mainly refer to can absorption, the inorganic particle of scattering or reflected sunlight, preferable alloy oxide particle, particularly preferably zinc oxide, titanium oxide.Wherein the weight ratio of silver-colored simple substance or silver compound and material that can shielded from light is 0.01 to 0.05, is preferably 0.02 to 0.04, most preferably is 0.035.If described weight ratio is for being less than 0.01, final products anti-microbial property is not good; If described weight ratio is for being greater than 0.05, because shell thickness is excessive, cause equally anti-microbial property not good.
Another aspect of the present invention provides the carrying silver antimicrobials product of a kind of composite particles that comprises described simple substance silver particles or silver compound as main component, wherein comprises as the simple substance silver particles of main component or composite particles and the dispersant of silver compound.In addition, the carrying silver antimicrobials product selectively the present invention relates to can also comprise other additives such as flavouring agent, surfactant.
The dispersant that wherein said carrying silver antimicrobials product comprises is selected from one or more in fatty alcohol of water, C1～C8 etc., is preferably water, methyl alcohol, ethanol and propyl alcohol.The ratio of water and alcohol there is no particular restriction, as long as can guarantee as the simple substance silver particles of main component or the composite particles of silver compound dispersed.
In described antibacterial agent product, as the simple substance silver particles of main component or the composite particles of silver compound and the weight ratio of dispersant, be 0.001-0.1, be preferably 0.01-0.05, most preferably be 0.03.If be less than 0.001 lower limit, antibacterial activity is not obvious; If be greater than 0.1 higher limit, antibacterial agent dispersion viscosity is excessive, and the easy plug nozzle of antibacterial agent cannot be used the method for sprinkling to carry out antibiotic finish to fabric fibre etc.In addition, being greater than 0.1 higher limit also may cause antimicrobial particles that the precipitation of reuniting easily occurs.
Another aspect of the present invention provides a kind of method of preparing the composite particles of described simple substance silver particles or silver compound, and the method comprises the following steps:
(1) preparation A solution: first sodium silicate is added in the mixed solvent of water and alcohol, with preparation sodium silicate mixed solution, wherein the mass percent concentration of sodium silicate is 1～50wt%, preferred 1～10wt%, all the other are water and alcohol, alcohol can be the fatty alcohol of C1～C8, preferred alcohol, propyl alcohol, volume ratio 100:1～the 1:1000 of alcohol and water, preferably 100:1～1:100, is particularly preferably 50:1～1:50.In above-mentioned mixed solution, add ether-containing key, hydroxyl, carboxyl or amino water soluble polymer, dissolve form siliceous stoste (being designated as A solution) completely.The mass percentage content of the water soluble polymer of described ether-containing key, hydroxyl, carboxyl or amino in A solution is 0～5wt%, preferred 0～2wt%, and described ether-containing key, hydroxyl, carboxyl or amino water soluble polymer are to be selected from one or more in polyethylene glycol, polypropylene glycol, poly-BDO, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethyene diamine, polyacrylamide and polyvinylpyrrolidone.If the content of the water soluble polymer of described ether-containing key, hydroxyl, carboxyl or amino, higher than 5wt%, easily causes A solution viscosity to increase, make the pressed powder product finally obtaining be difficult for disperseing.
(2) configuration B solution: B solution is a kind of Bronsted acid solution, this Bronsted acid can be organic acid, inorganic acid or strong acid-weak base salt, preferably inorganic acid or strong acid weak base salt, be more preferably selected from least one in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, ammonium chloride and ammonium sulfate.In B solution, the total concentration of contained Bronsted acid is 0.1～10mol/L, preferably 0.5～2mol/L.If wherein the total concentration containing Bronsted acid is less than 0.1mol/L, may be because the amount of the B solution using is excessive, cause the gradient concentration of silver-colored simple substance in end product or Ag-containing compound inhomogeneous, if the total concentration containing Bronsted acid is greater than 10mol/L, may cause in end product a large amount of silver-colored simple substance or Ag-containing compound exposed on final particle surface, and not be embedded in granule interior.
(3) in the situation that stirring, A solution is slowly added dropwise in B solution, because the sodium silicate solution as A solution itself is exactly highly basic, in dropping process, the pH of mixed solution can raise gradually, until pH value to 7～14 of final mixed solution are preferably 9～11, then constant temperature stirs certain hour, above-mentioned thermostat temperature is 25 ℃～250 ℃, be preferably 35 ℃～100 ℃, more preferably 45 ℃～80 ℃, constant temperature mixing time is 0.5～24 hour.
(4) after above-mentioned (1), (2) and (3) operation, gained reaction system is designated as C successively.
(5) for example, to the solution that is slowly added dropwise to silver ion in reaction system C, AgF solution, AgNO
3solution and AgClO
4solution, preferably AgNO
3solution, wherein the weight ratio of silica in the silver iron compound in the solution of silver ion and reaction system C (being obtained by sodium silicate conversion) is at 0.1:100 to 10:100.Under uniform temperature, stir certain hour, make silver ion be converted into silver-colored difficulty soluble salt or oxide or simple substance, the preferred silver halide of difficulty soluble salt, silver orthophosphate.25 ℃～250 ℃ of the reaction temperatures of aforesaid operations, are preferably 35 ℃～100 ℃, more preferably 45 ℃～80 ℃.Constant temperature mixing time is 0.1～24 hour.
(6) after above-mentioned steps operation, gained reaction system is designated as D successively.
(7) to add in D solution can shielded from light the precursor solution of material.The weight ratio that material that wherein can shielded from light and reaction system are designated as silver-colored simple substance in D or silver compound is 0.01 to 0.05.Material that can shielded from light mainly refers to here can absorption, the inorganic particle of scattering or reflected sunlight, preferable alloy oxide particle, particularly preferably zinc oxide, titanium oxide.The predecessor of material that can shielded from light be can be water-soluble chloride, nitrate, sulphate, acetate, be preferably zinc chloride, zinc nitrate, zinc sulphate, zinc acetate and titanium tetrachloride etc.
(8) after above-mentioned steps operation, gained reaction system is designated as E successively.
(9) in E solution, slowly add A solution, make the pH value of the mixed solution of A and E be adjusted to 7～14, then constant temperature stirs certain hour, and above-mentioned thermostat temperature is 25 ℃～100 ℃, is preferably 35 ℃～100 ℃, more preferably 45 ℃～80 ℃.Constant temperature mixing time is 0.5～24 hour.
(10) repeat the thickness that (7) and (9) operation can increase light shield material stratum granulosum, until the weight ratio of carrier in product, silver and material that can shielded from light reaches optimum.Centrifugation, washing, the dry pressed powder product that to obtain.
Beneficial effect
Simple substance silver particles involved in the present invention or the composite particles of silver compound have the advantages that the concentration at granule interior silver exists gradient to distribute, and can effectively prevent photochromicly, guarantee antibacterial persistence simultaneously, and have the wash durability of raising.Can there is very soon photochromism in simple substance silver particles or silver compound under illumination, and therefore normally flavescence blackening cannot be used in textile industry, and the stripping wash-out phenomenon of simple substance silver or silver ion also can be aggravated simultaneously, causes antibacterial persistence variation.And in an embodiment of the invention due to simple substance silver particles or silver compound are included in to the inside of composite particles according to the mode of certain concentration gradient distribution, avoided simple substance silver particles or silver compound to see that photochromic situation occurs light, therefore can there is not discoloration problem, simultaneously because simple substance silver particles or silver compound exist certain concentration gradient to distribute, therefore can discharge slowly, and can not affect antibacterial effect.Carrier used and material that can shielded from light in addition, abundant hydroxyl is contained on surfaces such as silica, titanium oxide, in fabric treatment procedure, by baking, can be combined in very securely by chemical bonding effect the surface of fabric, thereby improve the wash durability of antibacterial agent.
Accompanying drawing explanation
Fig. 1 is that the cold field emission scanning electron microscope of high-resolution and attached energy disperse spectroscopy of joining thereof carry out the spectrogram of chemical element to the particle making in Preparation Example 1;
Fig. 2 is the X ray diffracting spectrum of the particle of Preparation Example 1 preparation;
Fig. 3 a, 3b, 3c and Fig. 4 are respectively the transmission electron microscope of sample particle of Preparation Example 1 preparation as photo;
Fig. 5 is for being used the antibacterial agent of Preparation Example 10 to carry out the cotton inhibition zone width contrast photo after the washing of different number of times after antibiotic finish;
The antibacterial antiplaque agent performance comparison experiment that the antibacterial agent that Fig. 6 makes in Preparation Example 2 for contrast and Preparation Example 10 make;
Fig. 7 is the photo of photochromic effect comparative trial.
Embodiment
The exemplary embodiment of the present invention is described below with reference to the accompanying drawings, to help to understand the present invention.Following embodiment is only described the present invention by way of example.Clearly, those of ordinary skills can, in scope of the present invention and essence, carry out various accommodations and modification to the present invention.Need to be appreciated that, this invention is intended to be encompassed in the flexible and modification that appended claims comprises.
Experimental drug:
Zinc nitrate (analyzing pure): purchased from Tianjin great Mao chemical reagent factory;
PVP K-30 (PVP): purchased from Chemical Reagent Co., Ltd., Sinopharm Group;
Sodium silicate (analyzing pure): chemical formula Na2SiO39H2O, molecular weight 284.22, purchased from Tianjin BASF Chemical Co., Ltd.
Ammonium sulfate (analyzing pure): purchased from Beijing Kang Puhui dimension Science and Technology Ltd..
Absolute ethyl alcohol (analyzing pure): purchased from Hedong District, Tianjin red rock chemical reagent work
PEG400: chemical formula: HO (CH2CH2O) nH, mean molecule quantity 380 ~ 420, purchased from Tianjin Bo Di Chemical Co., Ltd.
Silver nitrate (analyzing pure): purchased from Chemical Reagent Co., Ltd., Sinopharm Group
Sodium hydroxide (analyzing pure): purchased from Tianjin northization glass purchase and sale center
Preparation Example
preparation Example 1
(1) preparation A solution: 10g sodium silicate (amounting to approximately 5 grams of silica effective contents) is added in the mixed solvent (water: ethanol=40:1, volume ratio) of 200g water and ethanol, and formation mixed solution stirs.Then in the mixed solution forming, add 3g polyethylene glycol, continue to be stirred to polyethylene glycol and dissolve formation siliceous stoste (being designated as A solution) completely, wherein the mass percent of polyethylene glycol in A solution is about 1.5%.
(2) configuration B solution: by ammonium chloride formation soluble in water B solution, wherein ammonium chloride concentration is 1.2mol/L.
(3) under stirring, A solution is slowly added dropwise in 200g B solution, in dropping process, by the pH value of pH detection paper mixed solution, until the pH value of final mixed solution is about 10 end, reacts, then at 55 ℃ of constant temperature, stir 12 hours.The end reaction system obtaining is designated as C.
(4) in reaction system C, be slowly added dropwise to 100 milliliters of 0.01mol/L (amounting to silver content 1.08 grams per liters) silver nitrate aqueous solutions (approximately 0.1 gram of silver content), the about 100:2 of weight ratio of silica and silver-colored simple substance particle or Ag-containing compound, then at 55 ℃ of constant temperature, stir 10 hours, make silver ion be converted into AgCl or simple substance Ag.The end reaction system obtaining is designated as D.
(5) under stirring, in D solution, add 6 milliliters of 6.2mol/L zinc chloride (zinc chloride content 839 grams per liters amount to zinc oxide content 500 grams per liters), (silver-colored simple substance particle or Ag-containing compound and zinc oxide weight ratio 3.5:100 continue to stir 5 hours.The end reaction system obtaining is designated as E.
(6) under stirring, in E solution, again slowly add A solution, with pH detection paper pH, until the pH value of the mixed solution of A and E is about 8, then 65 ℃ of stirrings of constant temperature are 6 hours.
(7) repeating step (5) and (6) three times, until the weight ratio of carrier in product, silver and material that can shielded from light reaches optimum.Wherein to reach optimum be to determine optimum weight percent by final products are carried out to visible ray illumination experiment to the weight ratio of carrier, silver and material that can shielded from light: by dry powder-shaped sample or powder sample is dispersed in water to magneton irradiates under solar simulator 24 hours under stirring, whether the naked-eye observation of take there is variable color as standard, and nondiscolouring is excellent.Centrifugation, washing, the dry solid white powder product that to obtain.
preparation Example 2
Except replace polyethylene glycol with poly-BDO in step (1), in step (5), with beyond zinc nitrate replacement zinc chloride, all the other steps flow charts are identical with Preparation Example 1.
preparation Example 3
Except replace silver nitrate aqueous solution with the AgF aqueous solution in step (4), in step (5), with beyond zinc nitrate replacement zinc chloride, all the other steps flow charts are identical with Preparation Example 1.
preparation Example 4
Except use AgClO in step (4)
4the aqueous solution replaces silver nitrate aqueous solution, and in step (5), with beyond titanium tetrachloride replacement zinc chloride, all the other steps flow charts are identical with Preparation Example 1.
preparation Example 5
Except replace ammonium chloride with phosphoric acid in step (2), in step (5), with beyond zinc nitrate replacement zinc chloride, all the other steps flow charts are identical with Preparation Example 1.
preparation Example 6
Except replace ammonium chloride with ammonium sulfate in step (2), in step (5), with beyond zinc sulphate replacement zinc chloride, all the other steps flow charts are identical with Preparation Example 1.
preparation Example 7
Except polyethylene glycol concentration in A solution in set-up procedure (1) is about 5wt%; The amount of silver nitrate in set-up procedure (4), makes the about 100:0.2 of weight ratio of silica and silver-colored simple substance particle or Ag-containing compound; In set-up procedure (5), the amount of zinc chloride, makes beyond silver-colored simple substance particle or Ag-containing compound and zinc oxide weight ratio 1.5:100, and all the other steps flow charts are identical with Preparation Example 1.
preparation Example 8
Except the amount of silver nitrate in set-up procedure (4), make the about 100:5 of weight ratio of silica and silver-colored simple substance particle or Ag-containing compound; In set-up procedure (5), the amount of zinc chloride, makes beyond silver-colored simple substance particle or Ag-containing compound and zinc oxide weight ratio 2:100, and all the other steps flow charts are identical with Preparation Example 1.
preparation Example 9
Except the amount of silver nitrate in set-up procedure (4), make the about 100:10 of weight ratio of silica and silver-colored simple substance particle or Ag-containing compound; In set-up procedure (5), the amount of zinc chloride, makes beyond silver-colored simple substance particle or Ag-containing compound and zinc oxide weight ratio 5:100, and all the other steps flow charts are identical with Preparation Example 1.
preparation Example 10 to 12: the preparation of antibacterial agent
preparation Example 10
Get the argentiferous particulate samples 0.3g making in Preparation Example 1 and be scattered in the dispersant that 10g water and ethanol forms, ultrasonic dispersion 10 minutes, obtains antibacterial agent of the present invention.
preparation Example 11
Except argentiferous particulate samples amount is 0.02g, all the other steps flow charts are identical with Preparation Example 10.
preparation Example 12
Except argentiferous particulate samples amount is 1g, all the other steps flow charts are identical with Preparation Example 10.
contrast Preparation Example 1
Except the disposable silver nitrate aqueous solution that adds fast of step (4), do not carry out step (6) and (7) simultaneously in addition, all the other steps flow charts are identical with Preparation Example 1.Both the particle process centrifugation, having been obtained by step (5), washing, the dry solid white powder product that to obtain.Silver-colored simple substance particle or silver compound random distribution in the final particle obtaining in this contrast Preparation Example, radially concentration gradient useless distributes.
contrast Preparation Example 2
Get argentiferous particulate samples 0.3g that contrast makes in Preparation Example 1 and be scattered in the dispersant that 10g water and ethanol forms, ultrasonic dispersion 10 minutes, obtains antibacterial agent of the present invention.
EXPERIMENTAL EXAMPLE
eXPERIMENTAL EXAMPLE 1: in particle, contained element determines
Get the sample of preparation in 1 gram of Preparation Example 1, be scattered in 100ml aqueous solution of nitric acid (compound method of aqueous solution of nitric acid: get content and be 63% red fuming nitric acid (RFNA) 50ml and add deionized water and be diluted to 100ml), 40 ℃ of water-bath sealings are soaked 3 days, make zinc oxide and silver stripping as much as possible completely in sample.Get 10ml supernatant, centrifugal removal solid particulate matter, is then diluted with water to (volumetric flask constant volume) after 500ml, as sample, carries out inductively coupled plasma method body spectrometer (ICP-AES) test.
ICP-AES test result: silver accounts for 0.89% of silver and the total amount of substance of zinc.
eXPERIMENTAL EXAMPLE 2: particle surface elemental composition is analyzed
With reference to figure 1, utilize the energy disperse spectroscopy (EDAX company, the U.S.) on the cold field emission scanning electron microscope of high-resolution (HITACHI S-4800) to be prepared the sample surfaces elemental composition analysis of preparing in embodiment 1.Silver element is not contained on result show sample surface, only contains silicon, zinc and oxygen.Illustrate that silver is wrapped in granule interior.Wherein spectrogram is processed:
Treatment Options: all elements (normalization) by analysis, number of repetition=4
eXPERIMENTAL EXAMPLE 3: the phenetic analysis of particle crystalline state
With reference to figure 2, final particle to Preparation Example 1 preparation carries out X-ray diffraction analysis (XRD), XRD spectra shows that there is peak the position that this sample is only approximately 25 degree at 2 θ (2-theta), and intensity a little less than, and in other position, there is no characteristic peak, therefore final particulate samples is noncrystalline state.
eXPERIMENTAL EXAMPLE 4: the analysis of particle shape
With reference to figure 3a to Fig. 3 c and Fig. 4, utilize transmission electron microscope (JEM-1400) to carry out form and image contrast (contrast) analysis, the aggregation that result show sample is random particle to the sample of Preparation Example 1 preparation.Because this sample is noncrystalline state (seeing the analysis result to sample XRD in EXPERIMENTAL EXAMPLE 3), therefore, the contrast of sample is mainly derived from the difference (the thick contrast of matter) of Atom of Elements in sample and thickness.Because silicon, zinc and silver-colored atomic number exist significant difference, be respectively 14,30 and 47, and silica is the skeleton that forms this material, the spatial distribution of silicon is uniform.The TEM picture of high-amplification-factor is presented at granule interior and exists size to be less than the darker particle of contrast of 10nm.Can prove that thus contrast difference is because silver is mainly distributed in due to the inside of particle.Sample image contrast exists the variation tendency of significantly deepening gradually to particle center from grain edges, and in this explanation particle, silver-colored simple substance or Ag-containing compound exist the concentration gradient increasing gradually to particle center from grain edges.
eXPERIMENTAL EXAMPLE 5: water-fastness experiment
(1) making of medium:
1. culture dish is carried out to autoclave sterilization processing;
2. take NaCl 2.5g, peptone 5g, beef extract 1.5g, agar 8g, measure 500mL water;
3. in beaker, add 400ml water, heating is boiled, and adds beef extract, sodium chloride, peptone, limit edged stirs, and once adds on a small quantity agar limit edged and stirs, and adds water and dilutes, until agar and water add completely, with sodium hydroxide, regulate PH=7 to 7.5, be transferred to conical flask, autoclave sterilization.
(2) antibacterial experiment pretreatment:
1. the rectangle cotton sheet of 5 wide 2cm of long 5cm of clip, is added drop-wise to the antimicrobial fluid of Preparation Example 10 preparations on each cloth sheet, and the antibacterial agent quality of each cloth sheet load is equated;
2. cloth sheet is put into 90 degree baking oven preheating 2min, then at 150 ℃ of oven for drying 10min, take out cloth sheet and wash, wash respectively 10 times 20 times 30 times 40 times 50 times;
3. become 3 little cloth sheets of equal circle to carry out antibacterial experiment each cloth shears of washing;
(3) antibacterial tests content:
1. the medium of preparation is spread upon in each culture dish uniformly;
2. in each culture dish, inject the staphylococcus aureus of same amount, it is evenly distributed;
3. washed little cloth sheet by water-soaked, stick the central authorities at culture dish;
4. culture dish being placed on to 37.5 degree in electrothermostat cultivates 24 hours.
Result is with reference to Fig. 5, in figure, shown without having washed with the spraying of washing through different number of times the cotton fungistatic effect of antibacterial agent of the present invention, even if can find out that the cotton that has sprayed antibacterial agent of the present invention is after washing 50 times, it still has obvious inhibition zone.Prove that antibacterial agent of the present invention has stronger water-wash resistance, after repeatedly washing, still can keep good fungistatic effect.
eXPERIMENTAL EXAMPLE 6: anti-microbial property contrast experiment
Fig. 6 is for being used the antibacterial agent making in contrast Preparation Example 2 and the antibacterial agent being made by Preparation Example 10 to carry out the cotton inhibition zone width comparison diagram after the washing of different number of times after antimicrobial treatment.In Fig. 6, in every group of correction data, left side light color post representative contrasts the data of the antibacterial agent making in Preparation Example 2, the data of the antibacterial agent product that the dark post representative in right side is made by Preparation Example 10.As can be seen from the figure the fungistatic effect that, the present invention contains the silver product that radially concentration gradient distributes is better than the silver-containing antibacterial agent of silver-colored simple substance particle or Ag-containing compound concentration random distribution.And along with the increase of washing times, inhibition zone width reduces gradually, illustrate that fungistatic effect weakens, but wash use after above for 40 times in contrast Preparation Examples 2, make the inhibition zone width of antibacterial agent become 1/6 while not washing, and after surpassing 40 washings, inhibition zone width no longer increases with washing times and further reduces, and illustrates that 40 washings have been the washing upper limit of using the antibacterial agent making in contrast Preparation Example 2 substantially.
And the antibacterial effect of the antibacterial agent making in Preparation Example 10 is after washing 40 times, 1/3 fungistatic effect in the time of still can keeping not washing, and continue to increase washing times, inhibition zone width can further reduce, even if illustrate and stand 40 washings, still have the antibacterial agent making in Preparation Example 10 to be in a large number deposited on cotton.And the test data that contrasts the antibacterial agent making and the antibacterial agent making in Preparation Example 10 in contrast Preparation Example 2 can be found out, along with the increase of washing times, more than the fungistatic effect of the antibacterial agent product distributing containing silver concentration gradient of the present invention is always the twice of antibacterial agent of silver-colored random distribution.Therefore antibacterial agent product of the present invention is more water-fastness, and antibacterial effect is more remarkable simultaneously.
The inhibition zone width of the antibacterial agent of contrast Preparation Example 2:
The inhibition zone width of the antibacterial agent of Preparation Example 10:
eXPERIMENTAL EXAMPLE 7: photochromic property experiment
Fig. 7 a be the dispersion liquid of the silica micro-particle that contains silver-colored simple substance or Ag-containing compound and photomask agent of preparation in Preparation Example 1 through the photo of Exposure to Sunlight in a week, in this particle, silver-colored simple substance or Ag-containing compound have the concentration gradient reducing gradually from center to edge concentration;
The dispersion liquid that Fig. 7 b is the silica micro-particle that contains silver-colored simple substance or Ag-containing compound and photomask agent of preparation in contrast Preparation Example 1 is through the photo of Exposure to Sunlight in a week, and in this particle, silver-colored simple substance or Ag-containing compound and photomask agent are randomly dispersed in particle in carrier silica;
Comparison diagram 7a and Fig. 7 b can find out, after Exposure to Sunlight in a week, of the present invention have in particle silver-colored simple substance or Ag-containing compound exists the dispersion liquid of concentration gradient there is no obvious variable color, and do not have the dispersion liquid of the particle of silver-colored simple substance or Ag-containing compound concentration gradient that obvious variable color occurs.
Claims (1)
1. a method of preparing the composite particles that comprises simple substance silver particles or silver compound, the method comprises the following steps:
(1) preparation A solution: 10g sodium silicate is added in the mixed solvent of 200g water and ethanol, wherein the volume ratio of water and ethanol is 40:1, formation mixed solution stirs, then in the mixed solution forming, add 3g polyethylene glycol, continue to be stirred to polyethylene glycol and dissolve the siliceous stoste of formation completely, be designated as A solution;
(2) configuration B solution: by ammonium chloride formation soluble in water B solution, wherein ammonium chloride concentration is 1.2mol/L;
(3) under stirring, A solution is slowly added dropwise in 200g B solution, in dropping process, by the pH value of pH detection paper mixed solution, until the pH value of final mixed solution is about 10 end, reacts, then at 55 ℃ of constant temperature, stir 12 hours, the end reaction system obtaining is designated as C;
(4) in reaction system C, be slowly added dropwise to 100 milliliters of 0.01mol/L silver nitrate aqueous solutions, the weight ratio 100:2 of silica and silver-colored simple substance particle or Ag-containing compound, then at 55 ℃ of constant temperature, stir 10 hours, make silver ion be converted into AgCl or simple substance Ag, the end reaction system obtaining is designated as D;
(5) under stirring, in D solution, add 6 milliliters of 6.2mol/L zinc chloride, silver-colored simple substance particle or Ag-containing compound and zinc oxide weight ratio 3.5:100, continue to stir 5 hours, and the end reaction system obtaining is designated as E;
(6) under stirring, in E solution, again slowly add A solution, with pH detection paper pH, until the pH value of the mixed solution of A and E is about 8, then 65 ℃ of stirrings of constant temperature are 6 hours;
(7) repeating step (5) and (6) three times, until the weight ratio of carrier in product, silver and material that can shielded from light reaches optimum; Wherein to reach optimum be to determine optimum weight percent by final products are carried out to visible ray illumination experiment to the weight ratio of carrier, silver and material that can shielded from light: by dry powder-shaped sample or powder sample is dispersed in water to magneton irradiates under solar simulator 24 hours under stirring, whether the naked-eye observation of take there is variable color as standard, and nondiscolouring is excellent; Centrifugation, washing, the dry solid white powder product that to obtain.
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| CN100450365C (en) * | 2004-06-23 | 2009-01-14 | 北京圣鑫泽房地产经纪有限公司 | Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions |
| CN100482385C (en) * | 2007-06-15 | 2009-04-29 | 北京化工大学 | Method for preparing silver/silicon dixoide nucleocapsid structure nano particles |
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| CN102210324B (en) * | 2010-04-09 | 2013-06-19 | 中国科学院海洋研究所 | Selective bactericide with composite nanoparticles as well as preparation and application thereof |
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