Background technology
The anti-microbial property of silver has been applied to a lot of fields, as bactericide, antiseptic dressing, purifier, ceramics etc.
At present, people are as follows to the understanding of the sterilization mechanism of silver: silver and sulfydryl in the pathogenic bacteria metabolic enzyme combine, and make enzyme deactivation, not energy metabolism and death of pathogenic bacteria; The peptide glycan reaction that exposes on silver and the bacteria cell wall forms the invertibity compound, makes it not advance cell to oxygen transport, stops the germ activity, causes its death; DNA base combination in silver and the pathogenic bacteria, silver ion forms cross-linked each other, causes the dna structure sex change, suppresses it and duplicates, and makes the pathogenic bacteria inactivation; Oxygen effect in silver and the water and air can produce reactive oxygen species, and these materials can destroy intracellular various important biomolecule macromolecule and film, also can form other activating oxide, destroys growth and the breeding of bacterium.
Along with the further investigation of people to silver-colored anti-microbial property, find that the anti-microbial property of silver and the valence state of silver have very confidential relation, the high more antibacterial ability of valence state of silver is strong more.Wherein divalence silver and trivalent silver bactericidal effect is 50~200 times of the silver-colored and argent of monovalence, and the sterilization speed of trivalent silver compound than silver-colored fast 240 times of monovalence (Soap/Cosmetics/Chemical Specialties, March, 1994, page52).In silver compound, silver peroxide contains trivalent silver, and silver peroxide itself contains active oxygen, so anti-microbial property is better than other compound of silver.U.S. Pat 6436420B1 discloses silver peroxide has been applied to content in the antibiotic fabric.But, if the silver peroxide powder is used as anti-biotic material, the silver peroxide powder often easily takes place self gathers the situation that forms bulk.
Active carbon is a kind of very good adsorbent, and it has the double grading of physical adsorption and chemisorbed, is widely used in the various aspects of worker, agricultural production.Particularly using very extensively with our the closely-related water purification field of living, also there is application in Japan in cosmetics.But present application all exists the defective that can not kill adsorbed microorganism.So, there is the people that silver and active carbon are studied, for example Chinese patent application 93106057.5 discloses a kind of silver-carrying bacteriostatic activated carbon, generates silver bromide on active carbon, and it is used for water purification; Chinese patent 93114907.X discloses a kind of preparation method of active carbon loading silver, and what generate on active carbon is silver iodide.BP GB2127389 discloses a kind of argentiferous preparation method of active carbon, and what wherein form is silver chlorate.Also have the people that silver and NACF are studied, Chinese patent 02115175.X discloses a kind of preparation method who contains the nano-Ag particles antibacterial active carbon fiber, but this patent does not disclose the chemical form of nano-Ag particles, infers it is argent according to its technology.Therefore, in the prior art, be loaded with the active carbon of silver bromide, silver iodide and argent, their antibiotic speed and effect all await further raising in actual applications, and they generally all use silver nitrate as raw material, in finished product, often bring a large amount of acid groups and other ion into, in use be unfavorable for the healing of wound.
Summary of the invention
The purpose of this invention is to provide a kind of silver carried bactericidal active carbon and preparation method thereof with strong antibiotic property.
For achieving the above object, technical scheme of the present invention is: a kind of silver carried bactericidal active carbon forms by containing absorbent charcoal material absorption silver peroxide.
The content of described silver peroxide is 0.001~20.0% of silver carried bactericidal active carbon dry weight.
Describedly contain woven cloth, nonwoven, felt and the fiber that absorbent charcoal material is selected from active carbon powder, particle or carrying active charcoal.
A kind of preparation method of silver carried bactericidal active carbon comprises the steps:
1) silver peroxide is joined in 5~80% aqua ammonia, 5~80% the glacial acetic acid or adhesive, stir, place;
2) active carbon being put into above-mentioned solution soaks; Maybe with this solution coat or spray on the active carbon, with distilled water rinsing, oven dry 5 minutes to 3 hours under 50~100 ℃ of conditions, promptly get silver carried bactericidal active carbon then.
Described adhesive is selected from copolymer, epoxy resin, white glue with vinyl, polyvinyl alcohol, polyurethane, gelatin or the alginates of esters of acrylic acid, esters of acrylic acid and vinyl acetate.
Described active carbon can be pure active carbon, also can be attached to the active carbon on other carrier, and the selection of its carrier is various, can be woven cloth, nonwoven, felt and fiber.
The final concentration of described silver peroxide solution is 0.01~10%.
Described silver carried bactericidal active carbon comprises powder, particle, paste, gel, membrane agent and the hydrocolloid agent that contains the silver carried bactericidal active carbon composition.
Described silver carried bactericidal active carbon can be used for daily necessities.
The described daily necessities that contains silver carried bactericidal active carbon is adult-incontinence articles, sanltary towel, baby paper diaper, underwear, clothes, shoe-pad, wallpaper, curtain, footwear or sofa or automobile lining cloth, bedding, filter screen filter cloth, agent of deodorising and sterilizing, removes mite agent, deodorizing sterilizing device, water purification installation and cosmetics.
The inventor studies show that, because silver carried bactericidal active carbon has strong anti-microbial property, can be used for preparing bactericide and antibiotic material in medical use.
Described antibiotic material in medical use is the medicine with woven cloth, nonwoven, felt and the fiber of silver carried bactericidal active carbon and medical dressing of producing thus and treatment wound.
The preparation method of a kind of silver carried bactericidal active carbon disclosed by the invention has realized on active carbon the purpose of evenly coating or absorption silver peroxide, silver peroxide is coated with securely or is adsorbed on the active carbon.Preparation method of the present invention, technology is simple, and the foreign ion amount of bringing into is very little, is suitable for industrial-scale production.Silver carried bactericidal active carbon provided by the invention has solved the low problem of argentiferous active carbon bacterium resisting performance in the prior art.Utilize the performance and the argentic strong anti-microbial property of charcoal absorption liquid, gas, when silver carried bactericidal active carbon is made surgical dressing, because active carbon has very strong absorption property, can adsorb diffusate, secretion, the slough of the surface of a wound and the stench that overflows effectively, but also has the high-efficiency broad spectrum anti-microbial property of silver peroxide, and have no side effect, it can make the surface of a wound in the microenvironment of dry and comfortable cleaning, play the effect of deodorizing, anti-inflammation, promotion wound healing, have tangible advantage compared with prior art.
Silver carried bactericidal active carbon is applied to prepare bactericide and antibiotic material in medical use field, has broad prospects.
Embodiment
Below by specific embodiment the present invention is elaborated.
Embodiment 1: silver carried bactericidal active carbon powder or particle and the preparation of having woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
(1) 10 gram silver peroxides is joined among 8% the Dilute Ammonia Solution 1000ml, after stirring, placing, obtain 1% silver peroxide solution.
(2) with active carbon powder or particle, and woven cloth, nonwoven, felt, the fiber of having active carbon, putting into 1% silver peroxide solution soaked 5 hours, use the distilled water rinsing, dried 5 minutes to 3 hours down at 70 ℃, obtain silver carried bactericidal active carbon powder or particle, and woven cloth, nonwoven, felt and the fiber of having silver-colored bactericidal active carbon.
Embodiment 2: silver carried bactericidal active carbon powder or particle and the preparation of having woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
(1) 20 gram silver peroxides is added among 15% the Dilute Ammonia Solution 1000ml, after stirring, placing, obtains 2% silver peroxide solution.
(2) with active carbon powder or particle, and woven cloth, nonwoven, felt, the fiber of having active carbon, putting into 2% silver peroxide solution soaked 5 hours, use the distilled water rinsing, dried 5 minutes to 3 hours down at 70 ℃, obtain silver carried bactericidal active carbon powder or particle, and woven cloth, nonwoven, felt and the fiber of having silver-colored bactericidal active carbon.
Embodiment 3: silver carried bactericidal active carbon powder or particle and the preparation of having woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
(1) 30 gram silver peroxides is added among 45% the glacial acetic acid solution 1000ml, after stirring, placing, obtains 1% silver peroxide solution.
(2) with active carbon powder or particle, and woven cloth, nonwoven, felt, the fiber of having active carbon, putting into 3% silver peroxide solution soaked 5 hours, use the distilled water rinsing, dried 5 minutes to 3 hours down at 70 ℃, obtain silver carried bactericidal active carbon powder or particle, and woven cloth, nonwoven, felt and the fiber of having silver carried bactericidal active carbon.
Embodiment 4: silver carried bactericidal active carbon powder or particle and the preparation of having woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
(1) 10 gram silver peroxides is added among 50% the polyacrylic resin solution 1000ml, after stirring, placing, obtains 1% silver peroxide solution.
(2) with active carbon powder or particle, and woven cloth, nonwoven, felt, the fiber of having active carbon, putting into 1% silver peroxide solution soaked 5 hours, use the distilled water rinsing, dried 5 minutes to 3 hours down at 70 ℃, obtain silver carried bactericidal active carbon powder or particle, and woven cloth, nonwoven, felt and the fiber of having silver carried bactericidal active carbon.
Embodiment 5: have the preparation of woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
The silver peroxide solution thatembodiment 1,2,3,4 is obtained is sprayed directly on woven cloth with active carbon, nonwoven, felt, the fiber, dried 5 minutes to 3 hours down at 70 ℃, obtain woven cloth, nonwoven, felt and fiber with silver carried bactericidal active carbon.
Embodiment 6: have the preparation of woven cloth, nonwoven, felt or the fiber of silver carried bactericidal active carbon.
In the silver peroxide solution thatembodiment 1,2 and 3 obtains, directly add polyacrylic resin, and then be applied on woven cloth, nonwoven, felt or the fiber that adheres to active carbon, dried 5 minutes to 3 hours down at 70 ℃, obtain woven cloth, nonwoven, felt or fiber with silver carried bactericidal active carbon.
Embodiment 7: the application of silver carried bactericidal active carbon powder in medical surgical dressing
Silver carried bactericidal active carbon powder electromicroscopic photograph as shown in Figure 1, the silver peroxide distribution uniform.The silver carried bactericidal active carbon powder directly is spread on the wound, cooperates again with common gauze wrapping, to wound can play antibiotic, inhale effect smelly, hemostasis, with the promotion wound healing.
Embodiment 8: the application of silver carried bactericidal active carbon in medical surgical dressing.
Shown in Fig. 2 A, the fiber that one ofembodiment 1,2,3,4,5 and 6 are prepared with silver carried bactericidal active carbon,antibiotic layer 2 as medical surgical dressing,nexine 3 addings promotion bioactivator of wound healing in medical surgical dressing comprises growth factor, collagen, hyaluronic acid etc. again, theskin 1 of medical surgical dressing is a separation layer, and above three-decker is made surgical dressing.Wherein, can play the excellent antibiotic deodorization as antibiotic layer with the fiber of silver carried bactericidal active carbon.
Embodiment 9: the application of silver carried bactericidal active carbon in medical surgical dressing.
Shown in Fig. 2 B, the fiber that one ofembodiment 1,2,3,4,5 and 6 are prepared with silver carried bactericidal active carbon,antibiotic layer 2 as medical surgical dressing is directly used in wound, and theskin 1 of medical surgical dressing is a separation layer, and above two-layer structure is made surgical dressing.Wherein, can play the excellent antibiotic deodorization as antibiotic layer with the fiber of silver carried bactericidal active carbon.
Embodiment 10: the application of silver carried bactericidal active carbon on adult-incontinence articles.
As shown in Figure 3, the innermost layer of adult-incontinence articles (promptly pressing close to one deck of human body skin) is cotton yarn layer ofcloth 1; The outside successively second layer is theantibiotic layer 2 that contains silver carried bactericidal active carbon nonwoven or fiber, andantibiotic layer 2 is made by one ofembodiment 1,2,3,4,5 and 6 prepared nonwoven or fiber with silver carried bactericidal active carbon; Outside successively the 3rd layer iswater accepting layer 3; Outside successively the 4th layer is antiseizednonwoven layer 4, and above four-layer structure is made the adult-incontinence articles that contains silver carried bactericidal active carbon.
Embodiment 11: prepare the antibiotic property gel with silver carried bactericidal active carbon.
Get the prepared silver carried bactericidal active carbon powder in one ofembodiment 1,2 and 3,, mix, be prepared into the antibiotic property gel with conventional method according to following prescription.
Silver carried bactericidal active carbon powder 1.000g
Carbomer 75.690g
Sodium carboxymethylcellulose 22.690g
Methyl hydroxybenzoate 0.570g
Nipasol 0.050g
Add up to 100.000g
Mentioned component is mixed, and (pH 6-7) supplies volume with distilled water, can behind the mixing.
The silver carried bactericidal active carbon powder, the weight ratio content in the antibiotic property gel is 1%.The gel of making can directly apply to wound as wound dressing, also can be used as bactericide coating or is adhered on medical appliance such as ostomy appliances, incontinence device or the device.
Embodiment 12: the application of silver carried bactericidal active carbon particle in purifier.
As shown in Figure 4, the silver carried bactericidal active carbon particle that one ofembodiment 1,2 and 3 are prepared is mounted in the fixednetwork 1 of purifier dialysis sheet or dialysis post, as the silver carried bactericidal activecarbon packing material 2 in the purifier.The active carbon of packing material can play organic effect in the adsorbed water, and active carbon is uploaded attached silver peroxide and can be played and kill action of microorganisms in the water.With the water that this kind purifier purified, the content of silver ion is controlled at below the 50ppb in the water, can reach the standard of U.S.'s drinking water.
Silver carried bactericidal active carbon, the mode that can also be coated with or mix is applied in the purifier.
Embodiment 13: the test of silver carried bactericidal active carbon in-vitro antibacterial.
Adopt silver carried bactericidal active carbon, respectively staphylococcus aureus, Candida albicans done the in-vitro antibacterial test, with the argent active carbon as experimental control.The result of the test of anti-candida albicans is as shown in table 1; The result of the test of anti-staphylococcus aureus is as shown in table 2.
Table 1: the result of the test of anti-candida albicans
| Sample | CFU/ml(5min) | 5min bacteriostasis rate (%) | CFU/ml(10min) | 10min bacteriostasis rate (%) |
| Silver carried bactericidal active carbon | 5.96×103 | 92% | 0 | 100% |
| The argent active carbon | 2.53×104 | 66% | 1.62×104 | 78.20% |
| Inoculum concentration | 7.45×104 |
Table 2: the result of the test of anti-staphylococcus aureus
| Sample | CFU/ml(5min) | 5min bacteriostasis rate (%) | CFU/ml(10min) | 10min bacteriostasis rate (%) |
| Silver carried bactericidal active carbon | 5.76×103 | 93% | 0 | 100% |
| The argent active carbon | 2.33×104 | 65% | 1.58×104 | 77.240% |
| Inoculum concentration | 7.25×104 |
Result of the test shows that the anti-microbial property of silver carried bactericidal active carbon is stronger than argent active carbon.