CN1159488C - Antibacterial flexible material containing nm silver and its preparing process and application - Google Patents

Abstract

The present invention discloses a nano-silver antibacterial flexible material. Ultrafine particle silver is attached between the base units or on the base units of the flexible material, the surface layer of the ultrafine particle silver is silver oxide, the core is metal silver, and the particle size is from 1 to 900 nanometers. The flexible material can be used for daily use for people, can be used to treat skin infections and skin superficial mycotic infections for patients with traumas, and can be used as a functional yarn for preventing and treating the infections of incisional wounds after the incision operations of surgical operations.

Description

The preparation method of antibacterial flexible material containing nm silver

The invention relates to a kind of antiseptic flexible material and manufacture method thereof, more particularly, is about a kind of antibacterial flexible material containing nm silver and manufacture method and application.

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 yarn of human body so far; But do not see breakthrough in the medicinal functional yarn of human body at Nonimplantation, the definition that main cause is to define this yarn must be carrier with the yarn, 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-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 odourproof fiber yarn and a manufacture method ", open day: disclose a kind of antimicrobial yarn in 18 days November in 1987, it is with acrylic fibers yarn 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, and 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.Antibacterial flexible material containing nm silver and manufacture method thereof and application

One of purpose of the present invention provides a kind of antibacterial flexible material containing and manufacture method thereof.

Two of purpose of the present invention provides a kind of antibacterial flexible material containing nm silver.

Three of purpose of the present invention provides a kind of manufacture method of antibacterial flexible material containing nm silver.

Four of purpose of the present invention provides a kind of application of antibacterial flexible material containing nm silver.

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

In antibacterial flexible material containing nm silver of the present invention, be attached with ultra micron silver between the elementary cell of flexible material or on the elementary cell, the superficial layer of ultra micron silver is a silver oxide, and core is an argent, and its particle diameter is 1～900 nanometer; Between the elementary cell of flexible material or the amount of the ultra micron silver that adheres on the elementary cell be 2～200 micrograms/centimetre², described elementary cell can be between fiber, between yarn or absorption micropore etc.

In antibacterial flexible material containing nm silver of the present invention, described flexible material can be fabric, yarn or the textiles that synthetic fiber, natural fabric constitute, and also can be that paper or other have the synthetic or natural material of adsorptivity.Described natural fabric can be cotton, fiber crops, silk, wool fibre and other fiber, and synthetic fiber can be terylene, acrylic fibers, polyamide fibre and other fiber; Can or be made into textiles with above-mentioned synthetic fiber, natural fabric spun yarn, described textiles can be woven fabric, knitted fabric and bondedfibre fabric; The described synthetic or natural material that other has adsorptivity can be polymer adsorbing material such as sponge and inorganic mineral material, as zeolite, diatomite etc.

Further, antibacterial flexible material containing nm silver of the present invention, wherein flexible material is a bondedfibre fabric, this bondedfibre fabric can be made by natural or synthetic fiber, between the yarn of bondedfibre fabric or on be attached with ultra micron silver, the superficial layer of ultra micron silver is a silver oxide, and core is an argent, and its particle diameter is 1～900 nanometer; If necessary, on bondedfibre fabric, also contain liquid, amount of liquid is 20～200% of a bondedfibre fabric weight, the preferred liquid amount is 40～100% of a bondedfibre fabric weight, described liquid is the mixture of water, organic solvent and water and organic solvent, and water can be distilled water or other medically acceptable water, the monohydric alcohol of the preferred lower paraffin hydrocarbon of organic solvent, as ethanol etc., certain described liquid also can be other medically acceptable additive.

The preparation method of antibacterial flexible material containing nm silver of the present invention, comprise padding finishing liquid, roll steps such as dried, drying, described padding finishing liquid comprises that flexible material with marshalling in deflector roll is immersed in treatment fluid, keeps the liquid level certain height, and flexible material is fully soaked into.

Further, the preparation method of antibacterial flexible material containing nm silver of the present invention, also be included in drying, make the step that adds liquid behind the product, the amount of liquid of adding is 20～200% of a bondedfibre fabric weight, and the preferred liquid amount is 40～100% of a bondedfibre fabric weight.

In the preparation method of antibacterial flexible material containing nm silver of the present invention, dressing liquid contains: (in 200 kilograms of flexible materials)

4～32 kilograms of silver nitrates, 12～45 liters of ammoniacal liquor,

Add water to 1000 liters.

Further, in dressing liquid, can also be added with 1～25 kilogram of glucose.

In the preparation method of antibacterial flexible material containing nm silver of the present invention, dressing liquid can contain (in 200 kilograms of flexible materials):

4～32 kilograms of silver nitrates, 12～45 liters of ammoniacal liquor,

0.6～3.2 kilogram in NaOH, 0.2～11 kilogram of glucose,

0.1～0.6 liter in nitric acid, surplus are that water amounts to 1000 liters.

The preparation method of antibacterial flexible material containing nm silver of the present invention comprises that with flexible material padding finishing liquid, pick-up rate is 40～90%, under air blast and exhausting condition, use the hot air circulation drying then, time is 1～6 minute, and temperature is 90～180 ℃, and guarantees sufficient oxygen.

Antibacterial flexible material containing nm silver 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.

In the present invention, if necessary, the processing method of some textile industries, paper-making industry and polymer adsorbing material manufacturing industry and inorganic material manufacturing industry routine be can also add, pre-treatment, bulk processing, fine finishining, post-treating and other steps comprised; Can certainly comprise in conjunction with the conventional knowledge of this specialty and omit one or more steps by actual conditions, as long as but can prepare product.

The antifungal mechanism of product of the present invention is:

The nonactive enzyme of organized enzyme

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 rice, 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 nonwoven cloth that applying nano silver fabrication techniques goes out is with a wide range of applications on the medicinal functional nonwoven 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 nonwoven cloth will start one and take turns new Industrial Revolution, will promote shooting up and developing of medicinal functional nonwoven fabric industry.

Antibacterial flexible material containing nm silver of the present invention (with the nonwoven fabric is example, and code name is WFB) is through test, and every index is as follows:

1, long-lasting:

Make extracorporeal bacteria inhibitor test with the WFB original without any processing through following 3 kinds of modes again after handling, the result confirms that treated WFB and its fungistatic effect of WFB 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) WFB steeps (changing water every day) through 45 days water logging.

2, broad spectrum activity:

(1) extracorporeal bacteria inhibitor test of WFB:

WFB 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 WFB original of not doing any processing and the WFB 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 WFB 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 Labs of the entire PLA of the Chinese People's Liberation Army.

The antibacterial result of WFB antimicrobial yarn and 8 kinds of antibacterials

WFB antimicrobial yarn and control group bacteriostatic diameter antibacterials WIC method drug sensitivity tests

In the big ring 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

2, WFB has excellent bacteriostasis property to the drug resistance pathogenic bacteria

WFB and 8 antibacterials are made extracorporeal bacteria inhibitor test to 28 pathogenic bacteria simultaneously, the result shows that WFB 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 WFB and these 8 antibacterials compares, and the bacteria resistance function that WFB has a clear superiority in to chemical sproof bacterial classification is described.

4, pharmacokinetic

With cavy and rabbit is subjects, and WFB is to skin acute toxicity test, irritant test, hypersensitive test.Test unit: hospital general's pharmacology section of Nanjing Military Command.Result of the test proof WFB avirulence, nonirritant, 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 7 kilograms of silver nitrates, be dissolved in 380 premium on currency, add 26 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix; The degreasing all cotton non-woven fabric that purchase is obtained fully soaks into padding finishing liquid, and pick-up rate is 60%; Roll nonwoven fabric after doing and enter that use hot air circulation drying, time in the drying case be 4 minutes, temperature is 130 ℃, and guarantees the oxygen of abundance; At last the nonwoven fabric behind drying is cut into the size that needs, sprays the distilled water of fabric weight 50% after the sterilization, airtight package.

Example 2

Take by weighing 18 kilograms of silver nitrates, be dissolved in 600 premium on currency, add 33 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix.The degreasing all cotton non-woven fabric that purchase is obtained fully soaks into padding finishing liquid, and pick-up rate is 80%; Roll nonwoven fabric after doing and enter that use hot air circulation drying, time in the drying case be 3 minutes, temperature is 160 ℃, and guarantees the oxygen of abundance; At last the nonwoven fabric behind drying is cut into the size that needs, sprays the distilled water of fabric weight 60% after the sterilization, airtight package.

Example 3

Take by weighing 13 kilograms of silver nitrates, be dissolved in 530 premium on currency, add 22 liters of concentrated ammonia liquors, get 2.8 kilograms of glucose, be dissolved in 100 premium on currency, adding water, to make its volume be 1000 liters, and mix, and all the other methods are with example 1.

Example 4

Take by weighing 30 kilograms of silver nitrates, be dissolved in 800 premium on currency, add 37 liters of concentrated ammonia liquors, get 4.8 kilograms of glucose, be dissolved in 100 premium on currency, add 0.25 liter of red fuming nitric acid (RFNA) again, 0.9 kilogram in NaOH, adding water, to make its volume be 1000 liters, and mix, all the other methods are with example 2.

Example 5

Take by weighing 10 kilograms of silver nitrates, be dissolved in 350 premium on currency, add 14 liters of concentrated ammonia liquors, get 0.6 kilogram of glucose, be dissolved in 50 premium on currency, add 0.35 liter of red fuming nitric acid (RFNA) again, 1.8 kilograms in NaOH, adding water, to make its volume be 1000 liters, and mix, all the other methods are with example 2.

Example 6

Take by weighing 15 kilograms of silver nitrates, be dissolved in 580 premium on currency, add 36 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix; The paper that purchase is obtained fully soaks into padding finishing liquid, and pick-up rate is 60%, and the paper behind the mangle enters and uses the hot air circulation drying in the drying case, time is 2 minutes, and temperature is 80 ℃, and guarantees sufficient oxygen, at last the paper behind drying is cut into the size that needs, sterilization back airtight package.

Example 7

Take by weighing 8 kilograms of silver nitrates, be dissolved in 400 premium on currency, add 18 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix; The paper substrate nonwoven fabric that purchase is obtained fully soaks into padding finishing liquid, pick-up rate is 80%, paper behind the mangle enters and uses the hot air circulation drying in the drying case, time is 3 minutes, temperature is 80 ℃, and guarantees sufficient oxygen, at last the paper behind drying is cut into the size that needs, spray the thimerosal of paper substrate nonwoven fabric weight 60% after the sterilization, airtight package.

Example 8

The concentration of spraying paper substrate nonwoven fabric weight 60% after sterilization is that all the other are with example 8 75% the ethanol.

Example 9

Except that adopting the polyster fibre based nonwoven, all the other are with example 1.

Example 10

Take by weighing 28 kilograms of silver nitrates, be dissolved in 800 premium on currency, add 38 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix; Purchase is obtained zeolite grind, make its particle diameter less than 30 microns, fully soak into dressing liquid then, entering afterwards again and using hot air circulation drying, time in the drying case is 6 minutes, and temperature is 160 ℃, and guarantees sufficient oxygen, airtight package.

Example 11

Take by weighing 10 kilograms of silver nitrates, be dissolved in 520 premium on currency, add 36 liters of concentrated ammonia liquors, adding water, to make its volume be 1000 liters, and mix; The degreasing all cotton fabric that purchase is obtained fully soaks into padding finishing liquid, and pick-up rate is 60%; Roll degreasing all cotton fabric after doing and enter that use hot air circulation drying, time in the drying case be 4 minutes, temperature is 130 ℃, and guarantees the oxygen of abundance; At last the degreasing all cotton fabric behind drying is cut into the size that needs, sprays the distilled water of fabric weight 40% after the sterilization, airtight package.

Claims (5)

1, a kind of preparation method of antibacterial flexible material containing nm silver, it is characterized in that comprising padding finishing liquid, roll steps such as dried, drying, described padding finishing liquid comprises that flexible material with marshalling in deflector roll is immersed in treatment fluid, keeps the liquid level certain height, and flexible material is fully soaked into; Described to roll dried pick-up rate be 40～90%, uses the hot air circulation drying then under air blast and exhausting condition, and the time is 1～6 minute, and temperature is 90～180 ℃, and guarantee sufficient oxygen, and described dressing liquid prescription is: (in 200 kilograms of flexible materials):

4～32 kilograms of silver nitrates, 12～45 liters of ammoniacal liquor,

1～25 kilogram of glucose adds water to 1000 liters.

2, a kind of preparation method of antibacterial flexible material containing nm silver, it is characterized in that comprising padding finishing liquid, roll steps such as dried, drying, described padding finishing liquid comprises that flexible material with marshalling in deflector roll is immersed in treatment fluid, keeps the liquid level certain height, and flexible material is fully soaked into; Described to roll dried pick-up rate be 40～90%, uses the hot air circulation drying then under air blast and exhausting condition, and the time is 1～6 minute, and temperature is 90～180 ℃, and guarantee sufficient oxygen, and described dressing liquid prescription is: (in 200 kilograms of flexible materials):

4～32 kilograms of silver nitrates, 12～45 liters of ammoniacal liquor,

0.6～3.2 kilogram in NaOH, 0.2～11 kilogram of glucose,

0.1～0.6 liter in nitric acid, surplus are that water amounts to 1000 liters.

3, the preparation method of antibacterial flexible material containing nm silver according to claim 1 and 2 is characterized in that described flexible material is a bondedfibre fabric.

4, the preparation method of antibacterial flexible material containing nm silver according to claim 3 is characterized in that also being included in drying, makes the step that adds liquid behind the product, and the amount of liquid of adding is 20～200% of a bondedfibre fabric weight.

5, the preparation method of antibacterial flexible material containing nm silver according to claim 3 is characterized in that described liquid is the mixture of water, organic solvent and water and organic solvent.