CN1147640C - Antibacterial fabric containing nm-class silver powder and its making method - Google Patents

Abstract

The present invention discloses a nano silver antibacterial fabric. Ultrafine particle silver is attached between the fibers or to the fibers of the fabric, the surface layer of the ultrafine particle silver is silver oxide, the core is metal silver, and the particle diameter is from 1 to 900 nanometers. The fabric can be used as an article for daily use for people, and can be used as the functional fabric for treating the skin infections and skin superficial mycosis infections for patients with traumas, and preventing and treating the infections of incisional wounds after the incision operations of surgical operations.

Description

The nanometer silver antimicrobial process for making such fabric

The invention relates to a kind of antiseptic fabric and manufacture method thereof, more particularly, is about a kind of nanometer silver antimicrobial fabric and manufacture method thereof.

Functional textile be this century the eighties at first propose by Germany scientist, and meet with a response in developed country rapidly, countries in the world have all been dropped into substantial contribution and have been researched and developed, and come out and are applied to clinical at portable existing procucts on the medicinal functional fabric of human body so far; But do not see breakthrough in the medicinal functional fabric of human body at Nonimplantation, the definition that main cause is to define this fabric must be carrier with the fabric, good stability, to the treatment of human body diseases ultra high efficiency, long-acting, low toxicity and auxiliary curing function or the like, the sort of anything but simple the sort of notion that sprinkles with the medicine dip-coating comes down to a kind of brand-new novel " stype ".

In the clear 54-151669 of Japan Patent, a kind of bactericidal properties cloth is disclosed, its compound resin solution independent or mixture that will contain copper, silver (6 microns of average grain diameters) is handled yarn, be made into bactericidal properties cloth again after making this solution evenly be coated on the surface of yarn, this product can be made the lining of rubber boot, canvas shoes and socks.

In Japan " process technology " vol.17 NO7 report, handle acrylic fiber with copper and sulfide, get acrylic fibers one copper sulfide compound, it has bacteriostasis to staphylococcus aureus, Escherichia coli, hay bacillus, the thread tinea alba bacterium of skin.

At Chinese invention patent CN87100231A, exercise question is " antibiotic deodorant fabric and a manufacture method ", open day: disclose a kind of antibiotic fabric in 18 days November in 1987, it is with acrylic fabric priority and Cu ⁺, Viride Nitens 4 composite crosslinkings, product has bacteria resistance function to 10 bacterial classifications such as staphylococcus aureus, MRSA, white Portugal coccus, Candida albicanss, it can be used as underwear, socks, shoe-pad and the medical industry of antibacterial deodourizing, the Work Clothes of food industry.

In the flat 3-136649 of Japan Patent, the applying date: disclose a kind of anti-bacteria cloth that prevents mastitis for milk cows in 24 days October in 1989.It is compound with the coordinate bond form with silver ion and polyacrylonitrile, and product has inhibitory action to 6 kinds of bacterial classifications such as streptococcus, staphylococcus, can be used as the anti-bacteria cloth of wiping cow breast nipple with the mammitis of prevention milk cow.

More than these products antibacterial action is all arranged, but antimicrobial spectrum is wide, effect is not obvious, and different fully with the present invention.

One of purpose of the present invention provides a kind of antibiotic fabric and manufacture method thereof.

Two of purpose of the present invention provides a kind of nanometer silver antimicrobial fabric.

Three of purpose of the present invention provides a kind of manufacture method of nanometer silver antimicrobial fabric.

These and other objects of the present invention will and be described and further set forth by following detailed description.

In nanometer silver antimicrobial fabric of the present invention, be attached with ultra micron silver between the fiber of fabric or on the fiber, the superficial layer of ultra micron silver is a silver oxide, and core is an argent, and the ultra micron silver granuel directly is 1～900 nanometer; Between the fiber of fabric or the amount of the ultra micron silver that adheres on the fiber be 2～200 micrograms/centimetre ²

The preparation method of long-acting wide-spectrum antiseptic nanometer silver fabric of the present invention comprises by the formulated finishing agent, then with fabric padding finishing liquid, is keeping using the hot blast drying under the sufficient oxygen condition then, washing, oven dry at last.

In the present invention, dressing liquid contains: (in 200 kilograms of fabrics)

5～30 kilograms of silver nitrates, 15～40 liters of ammoniacal liquor,

Add water to 1000 liters.

Further, dressing liquid also contains 1～20 kilogram of glucose.

Further, finishing agent of the present invention comprises: (in 200 kilograms of fabrics)

5～30 kilograms of silver nitrates, 15～40 liters of ammoniacal liquor,

0.8～3 kilogram in NaOH, 0.2～10 kilogram of glucose,

0.2～0.5 liter in nitric acid, surplus are that water amounts to 1000 liters.

In the present invention, with fabric padding finishing liquid, pick-up rate is 60～90%, uses the hot blast drying then under air blast and exhausting condition, and the time is 1～10 minute, and temperature is 90～200 ℃, repeatedly washs, pads, and pick-up rate is 100～150%, at last oven dry; Described drying can be the hot blast drying, also can be warm-up mill, radiation or Far-infrared Heating etc.

Product of the present invention can be used as medical (outward) material and the skin infection of treatment traumatic patient and the material of superficial skin fungus infection and prevention of surgical incision postoperative and treatment infection of incisional wound of treatment burn and scald, also can be used as daily living article.

The antifungal mechanism of product of the present invention is:

Ag ⁺Sulfydryl-SH easy and in the electronegative bacterioprotein combines, the organized enzyme loss of activity that some bacteriums are depended on for existence, thus reach fungistatic effect.

In the present invention, according to classical theory, silver has bactericidal action preferably, and sterilization mechanism is:

Silver is more stable material, substantially water insoluble, and the sterilizing power of itself and antimicrobial spectrum were both so wideless so by force yet, this is bad solution in macrocosm, so must in the microcosmos of nano science, seek answer, be applied to clinical in treatment of diseases and the prevention.The Nano Silver technology is the product that is based upon on quantum chemistry, materials chemistry, the biochemistry three big basic subjects, by with the granular on the material yardstick of silver, makes it reach 10 ^-9The nanometer scale of m, make full use of its skin effect, small-size effect and utilize various new specific physique and the effect that are different from macrocosm silver that it reflects, realize that it is long-lasting, broad spectrum activity, antibiotic strong, good stability, chance water effect not only do not weaken, the characteristic of Zeng Qianging and in killing the process of pathogenic bacteria on the contrary is not subjected to influence or the like the characteristic of human body acid-base degree.The penetrability of silver is strengthened simultaneously, promotes promoting regeneration of tissue for astringency, brings into play its treatment function.Because its surface area increases greatly, bigger variation also takes place in surface texture, and surface-activity strengthens greatly, and show high specific function, after testing, be 0.16～8.97 mg/ml to the MIC of pathogenic bacteria, MBC is 3.05～81.97 mg/ml, and its sterilizing ability has improved more than 200 times.

The Nano Silver fabric that applying nano silver fabrication techniques goes out is with a wide range of applications on the medicinal functional fabric of human body at Nonimplantation, is applied to go back preventable disease simultaneously body surface, the membrane disease except that being made into various antiseptic dressings; In addition, more extensive on the various antibacterial products Application and Development of human lives, work, as be made into various antibiotic clothes, bedding, socks footwear or the like textiles, light industrial goods and hospital equipment etc.We can say that the application of Nano Silver will make the human lives that the raising of a matter be arranged, Nano Silver medicinal functional fabric will start one and take turns new Industrial Revolution, will promote shooting up and developing of medicinal functional fabric industry.

Nanometer silver antimicrobial fabric of the present invention (hereinafter to be referred as LBDF) is through test, and every index is as follows:

1, long-lasting:

Make extracorporeal bacteria inhibitor test with the LBDF original without any processing through following 3 kinds of modes again after handling, the result confirms that treated LBDF and its fungistatic effect of LBDF original are constant substantially.

(1) washing is 50 times, washes clear water rinsing, totally 50 times by rubbing with the hands with soap is manual at every turn;

(2) washing is 100 times, only washes by rubbing with the hands totally 100 times with cleaning at every turn;

(3) LBDF steeps (changing water every day) through 45 days water logging.

2, broad spectrum activity:

(1) extracorporeal bacteria inhibitor test of LBDF:

LBDF is carried out MH flat board (or Colombia's agar plate or blood plate) extracorporeal bacteria inhibitor test, and identification of strains and drug sensitive test are with the French Vitek-32 of Biomerieux SA microorganism fully-automatic analyzer.Test specimen comprises the LBDF original of not doing any processing and the LBDF that handles through aforementioned (1), (2).The bacterial classification of extracorporeal bacteria inhibitor test comprises that gram-positive bacteria, Gram-negative bacteria, fungi and brood cell etc. amount to more than 40 pathogenic species.The result proves that LBDF shows obvious bacteria resistance function to these more than 40 bacterial classifications, and these more than 40 bacterial classifications remove that a few is arranged is the international standard bacterial strain, and great majority are bacterial strains of separating from patient's secretion, and its antibacterial difficulty is bigger.

Above extracorporeal bacteria inhibitor test is to be detected by prominent domestic units such as medicine test center Microbiological Lab of the entire PLA of the Chinese People's Liberation Army, Huashan hospital of Shanghai Medical Univ Bacteriology Rooms.

The antibacterial result of LBDF antibiotic fabric and 8 kinds of antibacterials

LBDF antibiotic fabric and control group bacteriostatic diameter antibacterials MIC method drug sensitivity tests

The big ring third of the negative benzene azoles ammonia benzyl cephalo cephalo cephalo celebrating of bacterium name source washing washing

Do not wash erythromycin

The 50 times 100 times husky stars of contrast XiLin, XiLin his pyridine mycin of azoles quinoline furan oxime

Staphylococcus aureus ATCC25923 20 18 18 7 24 S S S S S S S

Escherichia coli ATCC25922 15 14 14 7 10 S S S S S S

Pseudomonas aeruginosa ATCC27853 13 12 12 76 S S S

C.perfringens CMCC (B) 64,606 10

Staphylococcus aureus (MRSE) secretion 19 17 17 76 R R R R R R R

Staphylococcus epidermidis (MRSE) secretion 20 17 17 76 R R R R R R R

Micrococcus scarlatinae secretion 11 8876 S S S S S S S

Diplococcus gonorrhoeae secretion 11 10 10 7 31 S S S S S S

Escherichia coli secretion 17 15 15 76 R R R R R R

Enterobacter cloacae secretion 10 887 11 R R R R R R

Clostridium perfringen secretion 15 13 13 76 R R R R R R

Pseudomonas aeruginosa secretion 17 15 15 76 R R R R R R

Stenotrophomonas maltophilia secretion 16 13 14 76 R R R S R S

Acinetobacter bauamnnii secretion 15 12 12 7 19 R R R S S S

Klebsiella Pneumoniae secretion 17 14 14 76 R R R S R S

Serratia marcesens secretion 18 13 14 76 R R R R R S

Take labor ground citrobacter secretion 13 10 10 76 R R R R R R

Thunder amasss Pu Luoweideng bacterium secretion 15 13 13 76 R R R S R S

Aeromonas hydrophila secretion 13 11 13 7 16 R R R S R S

Aeromonas sobria secretion 14 12 12 7 17 R I I S R S

Vibrio vulnificus secretion 19 17 17 76 R R R S I S

Proteus mirabilis secretion 13 11 11 79 R R R S R R

Proteus vulgaris secretion 12 10 11 76 R R R S R R

Pan Shi proteus secretion 11 10 10 76 R R I S R S

Candida albicans secretion 23 21 21 76

Candida tropicalis secretion 20 17 17 76

Candida parapsilosis secretion 21 20 20 76

Torulopsis glabrata secretion 28 27 27 76

Annotate: S: responsive I: the R of intermediary: resistance

The blank AB fabric of bacterial strain MS fabric

Fabric is washed 20 sub-high pressures and is not washed height and compress and wash and wash for 20 times 50 times

Pseudomonas aeruginosa----17 14 17 18

Staphylococcus aureus----17 17 17 17

Escherichia coli----15 14 20 17

MRSA - - - - 16 14 18 17

Wax-shaped bacillus--11-15 15 15 17

Vibrio vulnificus----18 16 18 19

Candida albicans-21--13 11 11 13

B group hemolytic streptococcus----13 11 14 13

Pseudomonas Maltophilia----14 12 17 16

Nitrate-negative bacillus----16 15 15 17

Moscow' paratyphi C-12--14 16 21 16

Arizona bacterium----16 16 17 16

Citrobacter----16 16 17 15

Pneumobacillus----15 15 19 15

Hay bacillus----14 14 14 14

Morganella morganii--10-14 14 14 14

Alcaligenes faecalis----16 14 18 18

Si Shi Pu Tufeideng Salmonella----14 14 16 15

Enterobacter cloacae----15 15 15 15

Gonococcus----13 13 13 13

Above result shows, MS all has inhibitory action to 20 strain bacteriums, and the bacterium that commute develops immunity to drugs, as staphylococcus aureus persister (MRSA), Pseudomonas aeruginosa, Pseudomonas Maltophilia and nitrate-negative bacillus etc. all have inhibitory action, high pressure and wash 20 times and 50 times after all with without the washing the same, bacteriostasis there is not obvious influence, and new raising has been arranged, and the AB fabric can not suppress to above bacterium after washing 20 times, this shows that the two AB fabrics of MS fabric scope of restraining fungi extensively and not can influence fungistatic effect because of washing.

3, LBDF has excellent bacteriostasis property to the drug resistance pathogenic bacteria

LBDF and 8 antibacterials are made extracorporeal bacteria inhibitor test to 28 pathogenic bacteria simultaneously, the result shows that LBDF all shows tangible bacteria resistance function to 28 bacterial classifications, erythromycin only has bacteria resistance function to 8 bacterial classifications, Oxacillin (2), ampicillin (4), cephazoline (4), Zinacef (4), cefotaxime (15), gentamicin (6), Ciprofloxacin (14).

The extracorporeal bacteria inhibitor test that experimental results show that LBDF and these 8 antibacterials compares, and the bacteria resistance function that LBDF has a clear superiority in to chemical sproof bacterial classification is described.

4, pharmacokinetic

With cavy and rabbit is subjects, and LBDF is to skin acute toxicity test, stimulation test, hypersensitive test.Test unit: hospital general's pharmacology section of Nanjing Military Command.Result of the test proof LBDF avirulence, irritating property of nothing, no anaphylaxis.

5, clinical verification

Carried out clinical verification through after the above-mentioned test, existing existing:

(1) 50 clinical reports that a burn case of hospital general, Chinese People's Liberation Army Nanjing Burn and Plastic Surgery Dept. work.

(2) clinical report of the II class otch clinical follow of Jiangsu Prov. People's Hospital department of general surgery work.

(3) clinical report of the superficial skin fungus of Inst. of Dermatology, Chinese Academy of Medical Sciences's work.

Also have hospital of a few family that clinical testings such as skin-grafting area, tumour otch clinical follow, burn and scald, skin ulcer observation are carried out in addition.

Below further specify the present invention by specific embodiment, but embodiment only be used for the explanation, can not limit the scope of the invention.

In the present invention, if not refer in particular to, all parts, amount are the unit of weight based on gross weight.

Example 1

Take by weighing 8 kilograms of silver nitrates, be dissolved in 350 premium on currency, add 25 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix.With fabric padding finishing liquid, one soaks one rolls, and pick-up rate is 60%, uses the hot blast drying then under air blast and exhausting condition, and the time is 3 minutes, and temperature is 150 ℃, and four soak four and roll then, and pick-up rate is 100%, and oven dry promptly gets product of the present invention at last.

Example 2

Take by weighing 20 kilograms of silver nitrates, be dissolved in 650 premium on currency, add 35 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix.With fabric padding finishing liquid, one soaks one rolls, and pick-up rate is 90%, uses the Far-infrared Heating drying then under air blast and exhausting condition, and the time is 10 minutes, and temperature is 180 ℃, and four soak four and roll then, and pick-up rate is 120%, and oven dry promptly gets product of the present invention at last.

Example 3

Take by weighing 15 kilograms of silver nitrates, be dissolved in 550 premium on currency, add 25 liters of concentrated ammonia liquors, get 3 kilograms of glucose, be dissolved in 100 premium on currency, adding water, to make its volume be 1000 liters, and mix.With fabric padding finishing liquid, one soaks one rolls, and pick-up rate is 60%, heats drying with warm-up mill then under air blast and exhausting condition, and the time is 8 minutes, and temperature is 110 ℃, and four soak four and roll then, and pick-up rate is 100%, and oven dry promptly gets product of the present invention at last.

Example 4

Take by weighing 28 kilograms of silver nitrates, be dissolved in 750 premium on currency, add 35 liters of concentrated ammonia liquors, get 5 kilograms of glucose, be dissolved in 100 premium on currency, add 0.3 liter of red fuming nitric acid (RFNA) again, 1 kilogram in NaOH, adding water, to make its volume be 1000 liters, and mix.With fabric padding finishing liquid, one soaks one rolls, and pick-up rate is 60%, uses the radiation heating drying then under air blast and exhausting condition, and the time is 10 minutes, and temperature is 100 ℃, and four soak four and roll then, and pick-up rate is 100%, and oven dry promptly gets product of the present invention at last.

Example 5

Take by weighing 10 kilograms of silver nitrates, be dissolved in 350 premium on currency, add 15 liters of concentrated ammonia liquors, get 0.8 kilogram of glucose, be dissolved in 60 premium on currency, add 0.4 liter of red fuming nitric acid (RFNA) again, 2 kilograms in NaOH, adding water, to make its volume be 1000 liters, and mix.With fabric padding finishing liquid, one soaks one rolls, and pick-up rate is 90%, uses the radiation heating drying then under air blast and exhausting condition, and the time is 5 minutes, and temperature is 150 ℃, and four soak four and roll then, and pick-up rate is 100%, and oven dry promptly gets product of the present invention at last.

Claims (3)

1, a kind of preparation method of antibacterial fabric containing nm-class silver powder, it is characterized in that fabric padding finishing liquid, keeping under air blast and exhausting condition, using the hot blast drying under the sufficient oxygen condition then, time is 1～10 minute, temperature is 90～200 ℃, repeatedly washs, pads, and pick-up rate is 100～150%, oven dry at last, described dressing liquid prescription is: (in 200 kilograms of fabrics)

5～30 kilograms of silver nitrates, 15～40 liters of ammoniacal liquor,

1～20 kilogram of glucose adds water to 1000 liters.

2, a kind of preparation method of antibacterial fabric containing nm-class silver powder, it is characterized in that fabric padding finishing liquid, keeping under air blast and exhausting condition, using the hot blast drying under the sufficient oxygen condition then, time is 1～10 minute, temperature is 90～200 ℃, repeatedly washs, pads, and pick-up rate is 100～150%, oven dry at last, described dressing liquid prescription is: (in 200 kilograms of fabrics)

5～30 kilograms of silver nitrates, 15～40 liters of ammoniacal liquor,

0.8～3 kilogram in NaOH, 0.2～10 kilogram of glucose,

0.2～0.5 liter in nitric acid, surplus are that water amounts to 1000 liters.

3, the preparation method of antibacterial fabric containing nm-class silver powder as claimed in claim 1 or 2 is characterized in that described drying can be the hot blast drying, also can be warm-up mill, radiation or Far-infrared Heating etc.