CN110478533A - Medical discoloration antibacterial agent and its application - Google Patents
Medical discoloration antibacterial agent and its application Download PDFInfo
- Publication number
- CN110478533A CN110478533A CN201910842601.XA CN201910842601A CN110478533A CN 110478533 A CN110478533 A CN 110478533A CN 201910842601 A CN201910842601 A CN 201910842601A CN 110478533 A CN110478533 A CN 110478533A
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- Prior art keywords
- antibacterial
- medical
- organic
- discoloration
- dressing
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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Abstract
Change colour medical material the present invention relates to antibacterial, including various antibacterials change colour medical dressing, antibacterial changes colour suture, and change colour medical catheter and other antibacterials of antibacterial changes colour medical material.It is characterized in that material can be caused to change colour when the medical material containing antibacterial colour-changing agent and infection site contact.Organic anti-bacterial colour-changing agent has broad spectrum antibacterial performance, including at least one anti-Gram-negative bacteria or with a kind of resisting gram-positive bacteria dyestuff, or organic chromotropic dye and other anti-biotic materials combine, such as, organic chromotropic dye and quaternary ammonium salt are combined with silane end organic quaternary ammonium salt, organic off-color material and chitosan material combination, organic chromotropic dye and silver-containing material combine the antibacterial to be formed discoloration medical dressing, antibacterial discoloration suture, antibacterial discoloration medical catheter and other antibacterials discoloration medical material.The present invention gives its widely used organic anti-bacterial discoloration foam dressings and preparation method thereof.
Description
Technical field:
The invention belongs to the fields such as biomaterial for medical purpose, medical macromolecular materials, specifically one to work as medical antibacterial material
When material and infection site contact, discoloration can occur for antibacterial agent color and anti-microbial property is lasting, suitable for detecting and treating various senses
The medical discoloration antibacterial agent of the medical material of dye and wound and its application.
Background technique:
Medical dressing, suture, medical catheter and other medical materials are that medical very extensive consumptive material class produces
Product.Common medical dressing, suture, medical catheter and other medical materials all do not have antibacterial functions generally.It removes at present
Outside small part silver-containing antibacterial component product, the product of also some various other different antimicrobial components, such as chitosan in the market,
Triclosan, chlorohexidene etc., but these antibacterial components are without antibacterial color shifting properties, therefore research and develop and contain New-type wide-spectrum antibiotic property
Can, anti-biotic material adhesive force is strong, and the medical dressing of changeable colour, suture, medical catheter and other antibiotic material in medical use,
Especially widely used foam dressing, aerogel dressing, bearing hydrocolloid dressing and alginate dressing, for needing permanently effective treatment
Various acute chronic infectibilities and the wound that has infected, facilitate medical staff to judge dressing and wound infection situation, and
When more change dressings, effectively treatment controls various infected wounds, promotes wound healing, and meaning is extremely important.
Especially medical foam dressing rises emphatically in the negative pressure drainage Wound healing and bone regeneration of acute chronic wound treatment and prevalence
Make.Foam dressing is applicable in various acute and chronic Wound healing and bone regenerations.Particularly in the more wound care of diffusate, such as stern tail
Portion's pressure sore, sufficient leg ulcer, the burn of various degree, the nursing of skin donor site wound, postoperative wound and skin abrasion.Foam dressing with
Other functional dressings are compared, and are had the advantage that absorption wound exudate amount is big, are reduced replacement number.Avoid wound penetrating fluid
To the dipping of surrounding skin;Moist environment is provided for wound, makes wound not and will form incrustation, accelerating wound healing.Foam dressing
Physics be advantageous in that its soft comfortable and good permeability, keep the patient feels very comfortable, can be used for the big multiple location of body.
Foam dressing is mainly used for the more place of wound penetrating fluid, and this is also the situation of wound easy infection, bacterium meeting
Cause wound inflammation, wound infection inflammation seriously affects the healing of wound.It is therefore desirable to research and develop with good antibacterial function
It can and can show the dressing of wound infection degree, especially foam dressing.Regular-type foam dressing does not have antibacterial functions generally, to the greatest extent
Pipe also sells more some antimicrobial spume dressings at present in the market, but they are the foam dressing product containing silver ion mostly,
Such as contain silver nitrate, and nano silver, silver complex etc., and also these antimicrobial spume dressings are sprayed on the surface of foam dressing mostly
One layer of inorganic silver antibacterial agent is applied, but there are silver ions to discharge too fast and caducous problem for the foam dressing of surface load silver, makes
Dressing service life is short, and silver ion directly contacts skin in use, especially those uncontrollable silver ion rate of release
Ag-containing compound, influence the therapeutic effect of wound, side effect is obvious, can chromogenesis precipitating, it is serious to will lead to heavy metal
Poisoning, therefore, this kind of product cannot be used for a long time.This is for treatment large-area burns and chronic Hard agglut wound deep infection
Patient be have it is extremely challenging.
Summary of the invention:
The present invention is directed to shortcoming and defect existing in the prior art, and proposing one kind has broad-spectrum antibacterial action, and anti-
Bacterium consistency of performance leads to medical discoloration antibacterial agent and its application of discoloration when anti-biotic material is contacted with infection site.
A kind of medical discoloration antibacterial agent, it is characterised in that described organic comprising the organic dyestuff with broad-spectrum antibacterial action
Dyestuff is that the organic methylene of anti-Gram-negative bacteria and dimethylated methylene are blue, resisting gram-positive green (Brilliant Green),
Resisting gram-positive malachite green (malachite green), resisting gram-positive acridine yellow (Acriflavine), anti-leather are blue
Any one in family name's positive yellow (Quinacrine) and gentian violet (Gentian Violet);It also include antibacterial agent, antibacterial agent
Using containing organic quaternary ammonium salt or with silane end organic quaternary ammonium salt or contain Ag-containing compound complex compound compound nano silver.
Organic anti-bacterial dyestuff and organic dyestuff from primary colours becomes white, the side of facilitating when the location contacts of infection in the present invention
Just medical staff judges the observations of the infection conditions of wound, the preferred methylenum careuleum of organic anti-bacterial dyestuff (Methylene blue) and
Any one in gentian violet (Gentian Violet), additional amount are 2% or less.
The present invention is used when antibacterial agent containing organic quaternary ammonium salt or when with silane end organic quaternary ammonium salt, using organic quaternary ammonium salt or
Organosilan end quaternary ammonium salt and the low molecule caused, the organic quaternary ammonium salt of macromolecular structure or with organosilan end quaternary ammonium salt
Antimicrobial component, this combination further increase antibiotic anti-infection effect;Preferably,
3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3- (tri-methyloxysilyl
Propyldimethyloctadecyl ammonium) or zephiran, and contain and account for composition quality hundred
Divide 3- (trimethoxy silane base) the propyl-dimethyl octadecyl ammonium chloride or alkyldimethylbenzylammonium chlorination than 0.1-65%
Ammonium;Further preferably 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride or alkyldimethylbenzylammonium chlorination
It is 0.10%-25%, more preferably 0.12%-15% that ammonium, which accounts for composition quality percentage,.
The present invention can be provided only with 0.01% to 65% 3- (trimethoxy silane base) propyl-dimethyl octadecyl chloride
Change ammonium (3- (tri-methyloxysilyl propyldimethyloctadecyl ammonium);Or be provided only with 0.01% to
65% zephiran;Or equipped with 0.01 to 65% 3- (trimethoxy silane base) propyl-dimethyl 18
Alkyl ammomium chloride (3- (tri-methyloxysilyl propyldimethyloctadecyl ammonium) and 0.01 to
65% zephiran.
When antibacterial agent of the present invention uses Ag-containing compound complex compound compound nano silver;Select basic zirconium phosphate silver and sulfanilamide (SN) phonetic
Pyridine silver, this silver ion slowly can steadily release silver ion by ion exchange, and foam dressing silver content is
0.001%-1.5%, preferably 0.005%-0.1.0%, more preferably 0.05%-0.8%;When silver content is less than 0.001%,
Antibacterial effect is undesirable, conversely, when silver content is greater than 1.5%, although antibacterial effect has had reached 100%, antibacterial
Effect can't increase because content increases, and excessive silver ion can cause side effect to wound, in addition also increase and produce
Product cost.
The invention also provides a kind of methods of medical antibacterial discoloration foam dressing production, it is characterised in that passes through following step
It is rapid to obtain medical antibacterial discoloration foam dressing:
Directly by organic anti-bacterial dyestuff and various performed polymer raw materials, mixing is equal before catalysis is foamed in production foam process
Even, then plus the foam dressing containing organic anti-bacterial dyestuff is made in kicker, and wherein antibacterial chromotropic dye uses organic Asia
First indigo plant or gentian violet antibacterial dye or anti-Gram-negative dimethylated methylene are blue, resisting gram-positive green (Brilliant
Green), resisting gram-positive malachite green (malachite green), resisting gram-positive acridine yellow (Acriflavine),
Resisting gram-positive yellow (Quinacrine), additional amount is 2.0% hereinafter, the amount of being preferably added is 0.010%-0.22%;
When organic dyestuff is lower than 0.010%, antibacterial effect is undesirable, when organic dyestuff is higher than 2.0%, organic dyestuff antibacterial ability
Optimum value is had reached, excessive organic dyestuff increases the difficulty of solvent dissolution, also has an impact to the color comfort level of material;
Or,
Medical foam dressing is immersed in the liquid of organic dyestuff containing antibacterial, temperature control is at 15 DEG C -50 DEG C, and the time is from 2
Minute to 1 hour, then obtains required dressing, the organic dyestuff containing antibacterial by solvent evaporation foam-drying and post-processing
Liquid is made of the solvent of 2%-30% isopropyl alcohol and water or other dissolvable organic dyestuff, wherein foam dressing antibacterial color dyestuff
Content is 2.0% hereinafter, its ideal additional amount is 0.010%-0.22%.When organic dyestuff is lower than 0.01%, antibacterial effect
Undesirable, when organic dyestuff is higher than 2.0%, organic dyestuff antibacterial ability has reached optimum value, and excessive organic dyestuff increases
The difficulty of solvent dissolution, also comfortably has an impact to the color of material.
The invention also includes the methods of organic dyestuff and other anti-biotic materials combination production foam dressing.
For example, passing through coating or mist by spraying by organic quaternary ammonium salt or with silane end organic quaternary ammonium salt ion activity agent solution
Device is sprayed at the medical foam dressing surface of the chromotropic dye containing antibacterial, is attached to foam table by being chemically or physically crosslinked
Antimicrobial spume dressing is made through oven drying system in face.This method can be used for having had mature foam production processes technology, only
Antimicrobial spume product can be fabricated to by adjusting on the basis of original process;
Or,
Medical discoloration antimicrobial spume dressing is put into the molten of organic quaternary ammonium salt containing 0.01-0.8% or organosilan quaternary ammonium salt
Constant temperature impregnates in the reactive tank of liquid, and temperature is 15~50 DEG C;After immersion, by doctor's quaternary ammonium salt containing machine or organosilan season foam
Dressing takes out, and by spontaneously drying, infrared or oven drying, oven drying temperature is 35~80 DEG C, and drying time is 1~24 small
When;
Or,
Directly become by organic quaternary ammonium salt or with silane end organic quaternary ammonium salt ion and other antibacterials in production foam process
Then plus foaming agent dry forming color dyestuff is mixed with various performed polymers, is made containing organic quaternary ammonium salt or with silane end
The foam dressing of organic quaternary ammonium salt ion arrives medical antibacterial foam dressing finished product after being packaged, sterilizing.
The invention also includes the antibacterial discoloration foam dressings of preparation antibacterial chromotropic dye and argentiferous combination: in production foam work
Antibacterial dye and silver-containing material are proportionally added into performed polymer liquid in skill, stirred, kicker is added to be made
Foam dressing, anti-biotic material be crosslinked in foam dressing and pore, wherein silver-containing material be basic zirconium phosphateization silver and flamazine,
This silver ion slowly can steadily release silver ion by ion exchange, and foam dressing silver content is 0.001%-
1.5%, preferably 0.005%-0.1.0%, further preferred 0.05%-0.8%.When silver content is less than 0.001%, antibacterial effect
Fruit is undesirable, conversely, although antibacterial effect has had reached 100%, antibacterial effect is simultaneously when silver content is greater than 1.5%
It will not increase because content increases, and excessive silver ion can cause side effect to wound, in addition also increase product cost.
The invention also includes the suture containing above-mentioned discoloration antibacterial agent or medical catheters and other medical antibacterial materials
Material facilitates medical staff to understand the observation whether position infects, is beneficial to prevent wound by using above-mentioned discoloration anti-biotic material
Mouthfeel dye promotes wound healing, non-stimulated to skin, have no toxic side effect.
The sterilization method of antibacterial discoloration medical material is -60 irradiation sterilization of cobalt, electron beam irradiation or epoxy second in the present invention
One kind of alkane sterilization method.
Compared with prior art, the present invention being made by adding antibacterial chromotropic dye in foam dressing makes using discoloration
Dressing or suture made of antibacterial agent or medical catheter become white when contacting with infected wound, from primary colours, to understand
Wound infection situation helps medical staff and handles wound in time.The anti-dressing of antibacterial discoloration proposed by the invention is anti-with wide spectrum
Bacterium effect.Antibacterial chromotropic dye and other anti-biotic materials combine, such as organic quaternary ammonium salt or with silane end organic quaternary ammonium salt, and shell is poly-
Sugar or the combination of Ag-containing compound complex compound compound, such as basic zirconium phosphateization silver and flamazine, help to dissolve high score subgroup
At biomembrane, the effect of penetrating cell wall enhances effective antibacterial action (sterilization or inhibit bacterial growth etc.).This antibacterial becomes
Color dyestuff is particularly suitable for widely used foam dressing, treats acute chronic wounds, it is ensured that anti-microbial property is persistently effective, accelerates
Wound healing mitigates patient suffering.
Specific embodiment:
The following describes the present invention further through the description of specific embodiments, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.
Embodiment 1
6 grams of methanol are added to 50 grams of HYPOL Hydrogel (polyurethane prepolymer, W.R.Grace&Co
Trade (brand) name) in performed polymer (NCO content 0.5-1.2meg/g), ensured to be mixed thoroughly at several seconds, 44 grams of water, 0.015 gram
Methylene blue, 0.015 gentian violet and 1.2 grams of 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3- (tri-
Methyloxysilyl propyldimethyloctadecyl ammonium) or zephiran solution it is fast
Speed is added in HYPOL Hydrogel performed polymer mixed liquor, strong to stir, and is then 2.2 millis to mold thickness is entered foam solution
Foam, cured 2 hours through 37-55 degree, 30 minutes removings moisture of 100-120 degree in rice, it is cooling after acquisition antimicrobial spume dressing its
Density is 0.38g/cm3, it elongates and is fractured into 930%, liquid absorption amount 10.7g/g.
Embodiment 2
A, the preparation of performed polymer: by 1.0 parts of 3- (3 methoxy silane base) propyl-dimethyl octadecyl ammonium chloride, 8 parts of shells
Glycan, 40 parts of dehydration polyethylene glycol, 2 parts of glycerol, 30 parts of toluene di-isocyanate(TDI) mixing, stirring, 80 DEG C obtain for insulation reaction 1 hour
To thick performed polymer;
B, it foams: weighing 15 parts of polyether polyol, l parts of zinc octoates, 1 part of dimethylethanolamine, 3 parts of sodium alginates, 3 parts of silicon
Surfactant, 0.02 gram of methylene blue, 0.02 gentian violet part are uniformly mixed, quickly stir evenly, and pre-polymerization obtained by step A is added
Body, high-speed stirred 1 hour, pours into rapidly foaming mould after mixing and foams immediately, cures 25 hours and gathers to get antibacterial
Urethane dressing.
Embodiment 3
Medical foam dressing is put into different containing methylene blue, gentian violet and organic quaternary ammonium salt or organosilan quaternary ammonium salt
Constant temperature, which is impregnated, in the reactive tank of the solution of third alcohol and water contains 0.015% methylene blue until quaternary ammonium salt is adsorbed on dressing,
Until 0.015% gentian violet and 0.3% organic quaternary ammonium salt or organosilan quaternary ammonium salt, temperature is 15~50 DEG C;
After immersion, machine quaternary ammonium salt will be contained or organosilan season is taken out with foam dressing, through oven drying, drying temperature is
35~50 DEG C, last 30 minutes 100-110 degree.Dry total time is 1~24 hour.
Embodiment 4
Medical foam dressing is put into the solution containing methylene blue, gentian violet and sulfuric acid zirconates, liquid is by isopropanol
It being formed with the mixing of water, constant temperature, which is impregnated, in reactive tank contains 0.02% gram of methylene blue until being adsorbed on foam dressing, and 0.02%
Until gentian violet and 0.5% sulfuric acid zirconates, temperature is 15~50 DEG C;After immersion, foam dressing is taken out, through oven drying,
Drying temperature is 35~50 DEG C, last 30 minutes 80-110 degree.Dry total time is 1~24 hour.
Embodiment 5
By 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3- (tri- containing 2% concentration
Methyloxysilyl propyldimethyloctadecyl ammonium) solution passes through misty sprayer to medical foam
(MS-50PW 3mm is thick, liquid absorption amount 47.5g/100cm by dressing A2) on piece, through oven drying, drying temperature is 35~50 DEG C 30 points
Clock, last 30 minutes 80-100 degree.
Embodiment 6
By 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3- (tri- containing 2% concentration
Methyloxysilyl propyldimethyloctadecyl ammonium) solution passes through misty sprayer to medical foam
(MS-SS-60P, 3mm are thick, liquid absorption amount 52.2g/100cm by dressing B2) on piece, through oven drying, drying temperature is 35~50 DEG C 30
Minute, last 30 minutes 80-100 degree.
Embodiment 7
Killing staphylococcus aureus is carried out to embodiment 3,5,6 and with reference to the foam dressing of the standard sample containing nano silver,
Escherichia coli experiment, detects the sterilizing rate in different time.
According to embodiments of the present invention 3,5,6 and with reference to argentiferous standard sample provide polyurethane sponge dressing testing result
The polyurethane dressing of display, antibacterial provided by the present invention has good bactericidal property, and bactericidal property is more than or is equal to
Silver ion foam dressing.
Compared with prior art, the present invention by adding organic anti-bacterial off-color material or organic in production foam dressing
Off-color material and other anti-biotic materials are combined, such as are combined containing organic quaternary ammonium salt or with silane end organic quaternary ammonium salt, specifically
It says, by adding 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3- (tri-methyloxysilyl
Propyldimethyloctadecyl ammonium) or zephiran combination, organic anti-bacterial off-color material
It is combined with chitosan, organic off-color material and silver-containing material combination, more specifically, basic zirconium phosphate is silver-colored, flamazine makes to be obtained
The antibacterial discoloration foam dressing product obtained, which has, contacts discoloration and broad-spectrum antibacterial action with infected wound.
Similarly, antibacterial off-color material proposed by the invention is suitable for various medical dressing, suture, medical catheter
With other medical materials.The combination of antibacterial chromotropic dye or antibacterial chromotropic dye and other anti-biotic materials helps to dissolve macromolecule
The biomembrane of composition, the effect of penetrating cell wall enhance effective antibacterial action (sterilization or inhibition bacterial growth etc.), anti-microbial property
Persistently.
Claims (8)
1. a kind of medical discoloration antibacterial agent, it is characterised in that described to have engine dyeing comprising the organic dyestuff with broad-spectrum antibacterial action
Material is that the organic methylene of anti-Gram-negative bacteria and dimethylated methylene are blue, and resisting gram-positive green (Brilliant Green) resists
Gram-positive malachite green (malachite green), resisting gram-positive acridine yellow (Acriflavine), anti-gram
Any one in positive yellow (Quinacrine) and gentian violet (Gentian Violet);It also include antibacterial agent, antibacterial agent is adopted
With containing organic quaternary ammonium salt or with silane end organic quaternary ammonium salt or contain Ag-containing compound complex compound compound nano silver.
2. a kind of medical discoloration antibacterial agent according to claim 1, it is characterised in that organic dyestuff additional amount be 2% with
Under.
3. a kind of medical discoloration antibacterial agent according to claim 1, it is characterised in that contain organic quaternary ammonium when antibacterial agent uses
Salt or when with silane end organic quaternary ammonium salt, using 3- (trimethoxy silane base) propyl-dimethyl octadecyl ammonium chloride (3-
(tri-methyloxysilyl propyldimethyloctadecyl ammonium) or zephiran,
Containing accounting for composition quality percentage 0.1-65%.
4. a kind of medical discoloration antibacterial agent according to claim 1, it is characterised in that when antibacterial agent uses Ag-containing compound
When complex compound compound nano silver, basic zirconium phosphateization silver and flamazine, content 0.001%-1.5% are selected.
5. a kind of method of medical antibacterial discoloration foam dressing production, it is characterised in that containing such as claim 1- in foam dressing
Discoloration antibacterial agent described in any one of 4.
6. a kind of method of medical antibacterial discoloration foam dressing production according to claim 5, it is characterised in that by with
Lower content obtains:
Step 1: obtaining discoloration dressing, directly urging organic anti-bacterial dyestuff and various performed polymer raw materials in production foam process
It is uniformly mixed before changing foaming, then plus the foam dressing containing organic anti-bacterial dyestuff is made in kicker, or, by medical foam
Dressing is immersed in the liquid of organic dyestuff containing antibacterial, and temperature control is at 15 DEG C -50 DEG C, hour from 2 minutes to 1 time, then
Foam-drying is evaporated by solvent and post-processing obtains required dressing, and the liquid of organic dyestuff containing antibacterial is by 2%-30% isopropyl
Alcohol and water composition, wherein foam dressing antibacterial color dye content is 2.0% or less;
Step 2: the medical foam dressing with antibacterial effect is obtained, by organic quaternary ammonium salt or with silane end organic quaternary ammonium salt ion
Activator solution passes through coating or misty atomizers spray in the medical foam dressing surface of the chromotropic dye containing antibacterial, by chemistry
Or physics mode crosslinking is attached to foam surface, and antimicrobial spume dressing is made through oven drying system;Or, medical discoloration antibacterial is steeped
Foam dressing is put into constant temperature in the reactive tank of the solution of organic quaternary ammonium salt containing 0.01-0.8% or organosilan quaternary ammonium salt and impregnates, temperature
It is 15~50 DEG C;After immersion, doctor's quaternary ammonium salt containing machine or organosilan season are taken out with foam dressing, it is red by spontaneously drying
Outer or oven drying, oven drying temperature are 35~80 DEG C, and drying time is 1~24 hour.
7. a kind of method of medical antibacterial discoloration foam dressing production according to claim 5, it is characterised in that producing
The antibacterial agent that directly changes colour in foam process is added in prepolymer solution, stirs, and adds kicker that foam is made and applies
Material.
8. a kind of method of suture or medical catheter, it is characterised in that by being added such as in preparing raw material or semi-finished product
Discoloration antibacterial agent described in any one of claim 1-5 facilitates medical staff to understand the observation of infection site, is conducive to
It prevents wound infection, promotes wound healing, it is non-stimulated to skin, have no toxic side effect.
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CN1838970A (en) * | 2003-06-20 | 2006-09-27 | 庄臣及庄臣医药有限公司 | Antioxidant wound dressing materials |
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CN105451550A (en) * | 2013-07-01 | 2016-03-30 | 3M创新有限公司 | Antimicrobial foams and methods of making same |
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CN106902382A (en) * | 2017-02-08 | 2017-06-30 | 稳健医疗用品股份有限公司 | A kind of antibacterial medical dressing and preparation method thereof |
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CN1838970A (en) * | 2003-06-20 | 2006-09-27 | 庄臣及庄臣医药有限公司 | Antioxidant wound dressing materials |
US20070161936A1 (en) * | 2006-01-06 | 2007-07-12 | Svetlik Harvey E | Wound treatment-dressing and method of manufacture |
US20140275864A1 (en) * | 2013-03-15 | 2014-09-18 | Hydrofera, Llc | Polyurethane dressing and method for making same |
CN105451550A (en) * | 2013-07-01 | 2016-03-30 | 3M创新有限公司 | Antimicrobial foams and methods of making same |
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