CN101730515B - Method for producing hydrophilic foam dressing - Google Patents

Method for producing hydrophilic foam dressing Download PDF

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Publication number
CN101730515B
CN101730515B CN2008800211005A CN200880021100A CN101730515B CN 101730515 B CN101730515 B CN 101730515B CN 2008800211005 A CN2008800211005 A CN 2008800211005A CN 200880021100 A CN200880021100 A CN 200880021100A CN 101730515 B CN101730515 B CN 101730515B
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polyurethane foam
polyurethane
foam dressing
mentioned
preparation
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CN101730515A (en
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金原逸
张承完
金宇均
李享林
权五亨
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Wonbiogen Co., Ltd.
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WONBIOGEN CO Ltd
Industry Academic Cooperation Foundation of Kumoh National Institute of Technology
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Priority claimed from PCT/KR2008/003414 external-priority patent/WO2008156285A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A61F13/023—Adhesive bandages or dressings wound covering film layers without a fluid retention layer
    • A61F13/0243—Adhesive bandages or dressings wound covering film layers without a fluid retention layer characterised by the properties of the skin contacting layer, e.g. air-vapor permeability
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A61F13/0203—Adhesive bandages or dressings with fluid retention members
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F15/00—Auxiliary appliances for wound dressings; Dispensing containers for dressings or bandages
    • A61F15/008—Appliances for wound protecting, e.g. avoiding contact between wound and bandage
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/225—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/44—Medicaments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Disclosed herein is a method for producing a polyurethane foam dressing that protects injuries such as wounds or burns and is useful for wound healing. More particularly, the present invention provides a method for manufacturing a polyurethane foam dressing with remarkably improved productivity and processing efficiency, which can improve physical properties of the polyurethane foam dressing. The method comprises: preparing a moisture permeable waterproof polyurethane film layer; preparing a polyurethane prepolymer; preparing a polyurethane foaming mixture; obtaining a tacky gel type polyurethane foam layer; laminating the tacky gel type polyurethane foam layer on the polyurethane film layer; and winding the produced polyurethane foam dressing in a roll form and then ageing the foam dressing. The method further includes, impregnating the polyurethane foam with a moisturizer and drying the foam and, then, treating the foam with oxygen plasma to modify a surface of the foam dressing, thereby improving absorption rate of the foam dressing. The method of the present invention has advantages such as remarkably improved productivity and processing efficiency allowing mass production of foam dressings, thereby considerably reducing production costs and enabling supply of low cost foam dressings with improved physical properties.

Description

A kind of polyurethane foam dressing preparation method
Technical field
The present invention relates to a kind of polyurethane foam dressing preparation method of protecting the wound site such as wound, burn and helping wound healing; especially a kind of productivity and working (machining) efficiency that significantly improves foam dressing, and improve physical property new technology polyurethane foam dressing preparation method and with this polyurethane foam dressing that is prepared from.
Background technology
The processing of wound is the basis of medical science, has very long history.According to the record of papyrus (Papyrus) document, began to use animal oil or Mel, Cotton Gossypii etc. for the treatment of wound from B.C. 5000.Along with the development of history, the Wound healing and bone regeneration technology has also had a lot of change and progress.1962 zoologist Wen Te (Winter) deliver research paper and illustrate, compared with making the dry and incrustation of wound, keep that wound is moistening more to help its treatment, the effectiveness of the afterwards moistening processing of wound continues to have obtained demonstration and strengthens.Studies show that, prevent body fluid dehydration or the drying of wound secretion and keep moist dressing (Wet dressing) method of moist environment to help the treatment of wound.
Desirable dressing can keep the moist environment between wound and the dressing, has suitable water absorption and poisture-penetrability, prevents that wound surface is dry, prevents that surrounding normal skin from occuring rotten to the corn.In addition, need have breathability, prevent the functions such as outside bacterial invasion, and when change dressings, not be adhered to wound surface damage cambium.In addition, easily observe the Wound healing state, nonirritant, easy to use, economy is high, then can become desirable dressing.Be intended to develop the research and the effort that possess above-mentioned all ideal conditions dressing, still continuing so far.
Relatively the most recently used adjuvant has: disclosed at the beginning of the 1970's have " an OpSite TM", it is the semipermeability transparent membrane, can keep the moisture state of wound site, promotes the dissolving of slough and the formation of granulation tissue, helps Wound healing with this.But assemble excessive exudate in wound circumference, the skin erosion around making, and exudate is seeped into the outside, at any time discharge.
Nineteen eighty-two, the U.S. openly was referred to as " DuoDERM TM" product, it is hydrocolloid dressing, when being attached to wound site and exudate reaction form the moist environment of colloidal, promote the epithelization of wound.But the gas such as oxygen and carbon dioxide and steam are passed through, too much exudate is assembled, and when change dressings, colloid might be retained in wound surface.
Utilize high molecular dressing mainly to be prepared from by the gelation method, but also adopt foam preparation processes recently, make the synthetic high polymer such as polyurethane form perforate (OpenCell) through foaming.
United States Patent (USP) the 4th, 664, No. 662 (1985.7.31), United States Patent (USP) the 4th, 860, No. 737 (1983.8.11), United States Patent (USP) the 5th, 147, No. 338 (1991.6.17) etc., the polyurethane foam dressing that the medicines such as antibacterial such as hydrophilic polyurethane prepolymers, the water as foaming agent, nonionic surfactant and silver sulfadiazine that open mixing has 2 above terminal isocyanate groups are prepared from through foaming.The disclosed polyurethane foam dressing of above-mentioned patent, its general thickness is 0.5～20mm, moisture permeability is 300～5,000g/m 2/ 24hr (relative humidity 10～100%, 37 ℃), the perforate size is 30～700 μ m, and percent opening is 20～70%, and having outside thin layer thickness is the three-decker of 12.5～37.5 μ m.
In addition, United States Patent (USP) the 4th, 773, No. 409 (1985.9.20) and No. the 4th, 773,408, United States Patent (USP) (1985.9.25), disclosing its thickness is 1～10cm, density is 0.16～0.8g/cm 3Hydrophilic polyurethane foam dressing.The disclosed polyurethane foam dressing of above-mentioned patent, select sodium carboxymethyl cellulose, carboxymethylcellulose calcium, pectin, gelatin, guar gum, locust bean gum, collagen, karaya etc. as the hydrophilizing agent that can absorb moisture, and mix insoluble hydrophilic macromolecule Aqualon TMAnd can be from the Water Lock of Grain Processing company purchase TMDeng being prepared from.
Republic of Korea's patent discloses a kind of polyurethane foam dressing preparation method No. 0404140, and its mix and blend has the hydrophilic polyurethane prepolymers of terminal isocyanate groups and cross-linking agent, foaming agent, additive etc., injects afterwards mould and foams.But for polyurethane foam dressing being prepared into the product of desired thickness, need possess the mould of various shapes, size and specification, and because can only produce in a certain size individual mode, so production efficiency is low.
Republic of Korea's patent discloses another kind of polyurethane foam dressing preparation method No. 0553078, it foams the large moulds of injection such as hydrophilic polyurethane prepolymers and cross-linking agent, foaming agent, additive and obtains after the massive polyurethane foam, utilize horizontal guillotine to remove the top layer and also just be cut into certain thickness, follow independent lamination outside thin layer.But above-mentioned existing polyurethane foam dressing preparation method has the limitation of mould foaming.Namely, possess a certain size, in the mould of thickness and shape, disposable mixing possesses the hydrophilic polyurethane prepolymers of terminal isocyanate groups, as the water of foaming agent and other additives etc., through the foaming bulk product, again it is cut into certain thickness product and lamination outside thin layer, therefore need a plurality of techniques through being separated from each other, complicated process of preparation reduces productivity and the working (machining) efficiency of product greatly.In addition, foam immediately during mixing material in mould, pot life (Potlife) is restricted, and brings a lot of problems to molding.In addition, above-mentioned existing polyurethane foam dressing is larger because of the perforate of the face of itself and contact skin, so the exudate infiltration rate is very fast, but can be combined with the newly-generated skin histology of wound site, therefore causes pain or secondary damage when skin is removed dressing.
Therefore, the inventor once disclosed a kind of three-decker dressing in patent application 10-2005-0107898 number (No. the 716658th, patent) and 10-2006-0026887 number, comprising: anapsid thin polyurethane rete, separate external air and wound; The polyurethane foam intrinsic absorption layer is 1～600 μ m perforate of thin layer bottom, and its absorbing power is good; The wound surface contact layer for being formed at the trickle perforate of 1～50 μ m of intrinsic absorption layer bottom, can absorb exudate and have the non-tack of wound surface.Especially, above-mentioned patent improves productivity and the working (machining) efficiency of preparation foam dressing by a series of new preparation technologies for solving the problem that exists in the above-mentioned existing preparation method, it stirs after hydrophilic polyurethane prepolymers, water and the surfactant preparation foaming mixed liquor, utilize comma coating machine etc. to coat release paper with certain thickness and foam, then twine with the form of volume (Roll).
But, the inventor's above-mentioned patented technology, though significantly improve compared to prior art its productivity, but its pot life is restricted too, therefore approximately spend two hours to be as the criterion start-up time, the foaming mixed liquor on coating machine surface just begins to solidify, and As time goes on, the certain thickness product of more and more difficult production.In addition, the speed of polyurethane foam also is not enough to absorb smoothly exudate or blood.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and a kind of new polyurethane foam dressing preparation method is provided, it is by No. the 716658th, the patent improving the inventor and once applied for, especially patent application 10-2006-0026887 number method for sheet forming blank, thereby in the preparation method of the foam dressing with three-deckers such as thin layer, intrinsic absorption layer and wound surface contact layers, more simple and effective new preparation process be can pass through, productivity and working (machining) efficiency significantly improved.
Especially disclosed method among No. the 716658th, inventor's patent of once applying for and the patent application 10-2006-040708, because its pot life is restricted too, therefore approximately spend two hours to be as the criterion start-up time, the foaming mixed liquor on coating machine surface just begins to solidify, and As time goes on, the certain thickness product of more and more difficult production.Therefore another object of the present invention is to, solve the problem that exists in the above-mentioned existing method, a kind of new polyurethane foam dressing preparation method is provided, it is not subjected to the restriction of pot life, even the long-time continuous operation also can be produced certain thickness product, significantly improve workability.
Another purpose of the present invention is to provide a kind of new polyurethane foam dressing preparation method, and the comprehensibility that it improves prepared foam dressing especially by the surface modification of prepared polyurethane foam, significantly improves infiltration rate.
Other objects and advantages of the present invention will describe in the content below, and can further understand by enforcement of the present invention.
The object of the present invention is achieved like this: a kind of polyurethane foam dressing preparation method is provided, comprises:
(a) step of preparation anapsid waterproof polyurethane thin layer after 100 weight portion polyurethane resins add 20～70 weight portion methyl ethyl ketones and the mixing of 5～30 weight portion dimethyl formamides, is removed bubble, coats release paper and dry;
(b) step of polyurethane preformed polymer drops into isocyanates and reacts to the mixed solution that comprises polyhydric alcohol, dihydroxylic alcohols and antioxidant;
(c) step of preparation foaming synthetic is mixed 60～120 parts by weight of deionized water, 0.5～40 weight portion cross-linking agent and 1～10 weight portion surfactant as foaming agent;
(d) step of preparation foaming mixed liquor, to the polyurethane prepolymer that 100 weight portions are prepared from by above-mentioned (b) step, the foaming synthetic that mixed at high speed 50～150 weight portions are prepared from by above-mentioned (c) step;
(e) step of preparation polyurethane foam, to be supplied to by the foaming mixed liquor that above-mentioned (d) step is prepared from the release paper that tilts to fix by certain angle, it is foamed when dropping down under the inclined plane, to obtain 1～20mm thickness, has the colloidal polyurethane foam of sticking (Tack) property before the sclerosis;
(f) adjust the step of foam dressing thickness, the polyurethane foam that lamination is prepared from by above-mentioned (e) step and the anapsid waterproof polyurethane thin layer that is prepared from by (a) step, and the certain interval of being separated by pushes.
Preferably, a kind of polyurethane foam dressing preparation method of the present invention also comprises the step that increases infiltration rate, will impregnated in wetting agent by the foam dressing that above-mentioned (f) step is prepared from and carry out drying, or utilize oxygen plasma to process.In addition, a kind of polyurethane foam dressing preparation method of the present invention also can comprise maturation stage, will be positioned over air drier through the polyurethane foam dressing of above-mentioned lamination step and carry out ripening.In addition, also can comprise 0.01～20 weight portion medicine in the above-mentioned foaming synthetic.
In addition, the present invention also provides a kind of hydrophilic foam dressing preparation method to reach with this hydrophilic foam dressing that is prepared from, it comprises the step that increases infiltration rate, polyurethane foam dressing be impregnated in wetting agent and carries out drying, or utilize oxygen plasma to process.
Description of drawings
Fig. 1 to Fig. 4 is polyurethane foam dressing ideograph of the present invention;
Fig. 5 is the absorbed layer of polyurethane foam dressing of example 15 produced according to the present invention and the sweep electron microscope photo of wound surface contact layer;
Fig. 6 is the absorbed layer of polyurethane foam dressing of example 16 produced according to the present invention and the sweep electron microscope photo of wound surface contact layer;
Fig. 7 is the absorbed layer of polyurethane foam dressing of example 17 produced according to the present invention and the sweep electron microscope photo of wound surface contact layer;
Fig. 8 is the absorbed layer of polyurethane foam dressing of example 21 produced according to the present invention and the sweep electron microscope photo of wound surface contact layer;
Fig. 9 is the Medifoam-N of Ildong drugmaker as commercial product TMThe sweep electron microscope photo;
Figure 10 is the Medifoam-F of Ildong drugmaker as commercial product TMThe sweep electron microscope photo;
Figure 11 is the Smith﹠amp as commercial commodity; The Allevyn of Nephew company TMThe sweep electron microscope photo;
Figure 12 is the Carefoam as the Saeron drugmaker of commercial commodity TMThe sweep electron microscope photo;
Figure 13 is the Biatain as the Coloplast company of commercial commodity TMThe sweep electron microscope photo;
Figure 14 to Figure 16 is the curve chart of expression polyurethane foam dressing infiltration rate of the present invention;
Figure 17 is the state diagram of expression to the upper supply foaming of the fixing release paper 30A that tilts mixed liquor.
The specific embodiment
In this manual, " hydrophilic polyurethane " refers to have more hydrophilic polyurethane because importing hydrophilic group than general polyurethane.In addition, in the present invention, " moisture permeable film " refer to because of the hydrophilic polyurethane that will import hydrophilic group as raw material, more general polyurethane film has more the polyurethane film of poisture-penetrability.In addition, in this manual, " moisture-permeability waterproof thin film " refer to because of the hydrophilic polyurethane that will import hydrophilic group as raw material, have the polyurethane film of poisture-penetrability and water proofing property concurrently.
Polyurethane foam dressing preparation method of the present invention optionally or all comprises: the preparation process of moisture-permeability waterproof based polyurethane thin layer; The polyurethane prepolymer preparation process; Foaming synthetic preparation process; Foaming mixed liquor preparation process; Colloidal polyurethane foam and the thin polyurethane rete of property that lamination has sticking (Tack) also adjusted the step of foam dressing thickness; Increase surface modification step and the maturation stage of froth bed infiltration rate.
Below, each step is elaborated.
The preparation of moisture-permeability waterproof based polyurethane thin layer
Add after 20～70 weight portion methyl ethyl ketones and 5～30 weight portion dimethyl formamides stir to 100 weight portion polyurethane resins, remove bubble, coat release paper and dry, thus preparation anapsid waterproof polyurethane thin layer.At this moment, can add 1～10 weight portion pigment to above-mentioned polyurethane resin as required.In an embodiment of the present invention, be to utilize the vacuum stirring defoamer to carry out deaeration and remove bubble.Utilize coating thickness detector etc. to carry out drying after coating the polyurethane solutions of above-mentioned removal bubble on the inferior light release paper by certain thickness, then can obtain anapsid thin polyurethane rete.At this moment, if polyurethane resin is selected the polyurethane resin that has both poisture-penetrability and water proofing property, even select as the used polyurethane resin of the preparation of above-mentioned polyurethane foam, import the polyurethane resin of hydrophilic group at main chain, then can obtain to have both the moisture-permeability waterproof based polyurethane thin layer of poisture-penetrability and water proofing property.This thin polyurethane rete will form the outside of the dressing prepared according to the present invention.
The preparation of polyurethane prepolymer
Drop into isocyanates and react to the mixed solution that comprises polyhydric alcohol, dihydroxylic alcohols and antioxidant, thus polyurethane preformed polymer.
The concrete preparation example of polyurethane prepolymer is as follows: at first, drop into polyhydric alcohol and dihydroxylic alcohols and when stirring with the mixing speed about 150rpm, continue to stir 30 minutes after temperature risen to about 50 ℃, then drop into isocyanates and under condition of nitrogen gas until react till reaching the theoretical value of NCO content (%).
Above-mentioned polyhydric alcohol can separately or mix two or more following substances to be used: such as polypropylene oxide glycol (Polypropylene oxide glycol), the poly(ethylene oxide) glycol, polytetramethylene ether diol (Polytetramethylene ether glycol), the ethylene oxide/propylene oxide copolymer, PolyTHF/ethylene oxide copolymer, PolyTHF/propylene oxide copolymer, polybutylene carbonic ester glycol (Polybutylene carbonate glycol), polyhexamethylene carbonate diol, polycaprolactone glycol (Polycaprolactone glycol), poly-ethylidene adipic acid (Polyethylene adipate), the polybutylene adipic acid, poly-neopentyl adipic acid, poly-hexamethylene base adipic acid etc.
Preferably, the used polyurethane prepolymer of preparation polyurethane foam of the present invention is the hydrophilic polyurethane prepolymers that imports hydrophilic group.Ethylene oxide content as hydrophilic group when giving hydrophilic is most important, and this can be with reference to " Journal of Cellular Plastics 1976; 12; 285 ", " Journal of Cellular Plastics 1983; 19; 259 " the 4th, 008, No. 189 (1975.11.4) disclosed technology of the interior perhaps United States Patent (USP) that publishes.Therefore, best selecting for polyhydric alcohol has 2 above hydroxyls, molecular weight be 500～6,000 and ethylene oxide content be 20～90% ethylene oxide/propylene oxide copolymer.
Above-mentioned isocyanates can be selected aromatic series, aliphatic and set of permutations isocyanates or its mixture.For example, can separately or mix two or more following substances uses: such as 2, the 4-toluene di-isocyanate(TDI), 2, the 6-toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, 1, the 5-naphthalene diisocyanate, the tolidine vulcabond, hexa-methylene-1,6-vulcabond (Hexamethylene-1,6-diisocyanate), the isophorone vulcabond, XDI, cyclohexane extraction-1,4-vulcabond (Cyclohexylene-1,4-diisocyanate), lysinediisocyanate, tetramethylene-XDI etc.Preferably, select isophorone vulcabond, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI) and methylenediphenyl diisocyanates etc.
Above-mentioned diatomic alcohol compounds is independent or mix two or more following substances uses: such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, triethylene glycol (triethylene glycol), diethylene glycol, TEG, dipropylene glycol, dibutylene glycol, dimethyltrimethylene glycol, 1,4-cyclohexanedimethanol, 2-methyl isophthalic acid, 3-pentanediol etc.Preferably, separately or mix two or more ethylene glycol, propylene glycol and BDO and use.Diatomic alcohol compounds plays the effect of cahin extension agent (Chain Extender) in prepolymer, increase the prepolymer molecular weight, improves hard segment content, to improve mechanical properties.If but excessive use is then difficult even with the compound that foams when mixed liquor is foamed in preparation because of the viscosity increase of prepolymer, therefore should not excessive use.In addition, if the viscosity after synthetic is too high, when then after mix and blend polyurethane prepolymer and foaming synthetic, being supplied on the inclination release paper, because of the not good enough not easy-formation of flowability.Otherwise, if viscosity is excessively low, then because of too fast in inclination release paper trickling, also easy-formation not.Preferably, adding the synthetic prepolymer viscosity of diatomic alcohol compounds is 3,000～20,000cps (30 ℃).And various equivalent modifications can easily be regulated above-mentioned viscosity according to situations such as foaming mixture viscosity and forming temperatures.
In addition, when preparation polyurethane prepolymer of the present invention, also can add published additive by published method.Especially comprise antioxidant in these additives.Above-mentioned antioxidant is separately or mix two or more following substances and use it: such as Phenyl beta naphthylamine, the cysteine hydrochloride, dibenzylatiooluene, nordihydroguaiaretic acid, butylated hydroxyanisole (BHA), phosphoric acid, citric acid, ascorbic acid, arabo-ascorbic acid, the IRGANOX 1010 of propyl gallate and Ciba Specialty Chemicals company, IRGANOX 1035, IRGANOX 1076, IRGANOX 1330, IRGANOX 1425WL, IRGANOX3114, IRGANOX B215, IRGANOX B220, IRGANOX B225, IRGANOX B561, IRGANOX B313, IRGANOX B501W, IRGANOXB900, IRGANOX B1411, IRGANOX B1412, IRGANOX PS800, IRGANOX PS802, IRGAFOS P-EPQ etc.Preferably, separately or mix the uses such as two or more phosphoric acid, citric acid, dibenzylatiooluene, butylated hydroxyanisole (BHA), IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1330.Antioxidant can account for 0.05～5 % by weight of whole polyurethane prepolymers.
The preparation of foaming mixture
The preparations such as mixing water, cross-linking agent, surfactant can be used as the foaming mixture that foaming agent uses.Foaming mixture comprises 60～120 parts by weight of deionized water, 0.5～40 weight portion cross-linking agent, 1～10 weight portion surfactant, and also can comprise as required 0.01～2 weight portion pigment, 0.01～20 weight portion medicine, 0.1～40 weight portion wetting agent and absorb adjuvant.
Cross-linking agent can separately or mix the uses such as two or more glycerol, trimethylolpropane, BT, sorbic acid.Cross-linking agent improves the effect of foam mechanical physical property by cross-linking reaction when polyurethane foam molding.
Surfactant can be by openly purposes and method are used published surfactant.For example, F-68, F-87, F-88, F-108, F-127 as the BASF AG of ethylene oxide/propylene oxide block copolymer are arranged, and as L-580, the L-603 of silicon class surfactant, L-688, L-5420, SZ-1703, L-6900, L-3150, Y-7931, L-1580, L-5340, L-5333, L-6701, L-5740M, L-3002, L-626 etc.Surfactant plays wound surface contact layer 11 and the pore opening of intrinsic absorption layer 12 and the effect that pore is opened rate of regulating polyurethane foam dressing.Especially, as the F-68 of the BASF AG of ethylene oxide/propylene oxide block copolymer, helping in the situation that do not injure that tissue cleans a wound and nontoxic, is best surfactant therefore.
In the present invention, wetting agent plays keeps the wound surface moist environment, suppresses incrustation, helps Wound healing.Therefore, in the present invention, " wetting agent " not only comprises published general wetting agent, also comprises and can keep the wound surface moist environment, suppresses incrustation, helps the Wound healing and bone regeneration adjuvant of Wound healing.These wetting agents specifically have the alginic acid propylene glycol, methylcellulose, sodium carboxymethyl cellulose, carboxymethylcellulose calcium, carboxymethyl starch sodium sodium, sodium alginate, ammonium alginate, potassium alginate, calcium alginate, sodium caseinate, guar gum, locust bean gum, xanthan gum, cyclodextrin, Radix Acaciae senegalis, gellan gum, carrageenan, karaya, casein, tara gum, tamarind gum, Tragacanth, pectin, glucomannan, ghatti gum, arabinogalactan, Furcellaran, amylopectin, glucamine, carboxymethyl cellulose, chitin, chitosan, sodium alginate, hyaluronic acid, aminoacid, L-Aspartic acid, L-Aspartic acid sodium, DL-Alanine, the L-isoleucine, cetirizine hydrochloride, glycine, glycerol, L-glutaminate, Pidolidone, Pidolidone sodium, pyrimidine acid (Pyridine acid), L-threonine, sericin, serine, TYR, heparin, sodium chondroitin sulfate, sodium alginate, gelatin etc. can be contained in the above-mentioned foaming mixed liquor according to published capacity and method in above-mentioned scope.
In wetting agent, if cellulose family additives such as use carboxymethyl celluloses, the product that then can more not add improves the product mechanical properties.Namely play the effect of filler, and filler refers to add with anti-aging in the practical process of rubber or plastics, improve the material of intensity and weight etc.For example, on carbamide formalin resin or carbolic acid formalin resin or synthetic leather, during the molded polyurethanes thin film, obtain enough intensity because not depending merely on resin, therefore add fiber, asbestos, wood powder etc. and resin that the processing machinery physical property is strengthened.
In the present invention, " medicine " comprises the medicable published medicine of wound tool and antibacterial, but also comprises the Wound healing and bone regeneration adjuvant with bacteriostasis or granulation proliferation function.Therefore, in the present invention, the saccharide with bacteriostasis and granulation proliferation function also can be contained in the medicine.Such saccharide has sucrose, sorbic acid, mannitol, fructose, glucose, xylitol, lactose, maltose, maltose alcohol, trehalose etc., and the Wound healing and bone regeneration adjuvant with granulation proliferation function has fiber subcellular fraction multiplicaiton factor (FGF), liver fibronectior (HGF), the epidermal cell proliferation factor (EGF) etc.
Said medicine especially can comprise the natural materials with antiinflammatory action, antibacterial action, antifungic action or skin regeneration effect.These materials comprise: bioflavonoids, from tea tree oil, Radix Sophorae Flavescentis extract, orris extract, Radix Glycyrrhizae extract, grapefruit (seed) extract; Naringin; Polypeptide; Asiatic acid is from tocopherol, Herba Centellae; Extraction is from the natural materials from plant such as the beta glucan of Madecassic acid, mushroom, neem extract, Radix Hamamelidis Mollis extract, allantoin, Herba portulacae extract, poncirus trifoliata extract, phytosphingosine, Aloe extract.These natural materials can be according to published capacity and method, in above-mentioned scope separately or mix two or more being contained in the said mixture.
In addition, infection and propagation for preventing various pathogenic bacterias can comprise published antibacterial in the medicine.For example, silver sulfadiazine, povidone iodine, iodine, iodide ion salt, sulphuric acid fradiomycin, the sharp promise of Acker, chlorhexidine, Benzene Chloride diformazan hydrocarbon ammonium, Benzene Chloride ethyl ammonium, fusidic acid and its esters etc., can according to published capacity and method, in above-mentioned scope, be contained in the said mixture.
In addition, can according to the purpose for the treatment of and prevention, published other medicines be contained in the dressing of the present invention.
In addition, in order to increase the absorbability of polyurethane foam, in said mixture, can in above-mentioned scope, comprise the absorption adjuvant such as published high-absorbable macromolecule.
In addition, in foaming mixture of the present invention, add on a small quantity the published additives such as stabilizing agent, preservative agent, physical property regulator according to known purpose.
The preparation of foaming mixed liquor and the molding of polyurethane foam
In the 100 weight portion polyurethane prepolymers that are prepared from by above-mentioned steps, after high-speed stirred 50～150 weight portion foaming mixtures, should be to pressing on the fixing release paper 30A of certain angle inclination.The foaming mixed liquor of supplying foams when dropping down under the inclined plane, to form polyurethane foam.Preferably, the release paper of this moment is as the criterion with the straight line of supply foaming mixed liquor, tilts fixing to keep the angle of 30～70 degree.If the angle of inclination of release paper is below 30 degree, because the foaming mixed liquor is difficult for lower dropping down, therefore easy-formation not, and if more than 70 degree, then too fast along dropping down under the inclined plane because of the foaming mixed liquor, so also easy-formation not.In the present invention, because the mixed liquor that will foam by above-mentioned inclined plane is supplied on the release paper, therefore not limited by pot life, can produce continuously certain thickness product.Figure 17 is that expression is to pressing the upper state diagram of supplying the foaming mixed liquor of the fixing release paper 30A of certain angle d inclination.
The froth bed of above-mentioned molding preferably, during the colloidal state of the viscosity before having sclerosis, carries out next step lamination operation.Namely, after the state forming polyurethane foam with viscosity with thickness as colloid on the release paper, directly carry out the lamination with the thin polyurethane rete, need not like this to use other independent techniques of binding agent or adhesive etc., can finish simply lamination, to improve process efficiency.
Preferably, in this step release paper is selected macromolecule membrane or the stationery release paper of processing through silicon face.
Lamination (preparation of polyurethane foam dressing)
Polyurethane foam and thin polyurethane rete that lamination is prepared from by above-mentioned steps, and the certain interval extruding of being separated by, thus foam dressing thickness adjusted.At this moment, as mentioned above, lamination need not other binding agent or adhesive, and lamination has polyurethane foam and the thin polyurethane rete of the colloidal state of the viscosity before solidifying simply.But laminating method of the present invention is not limited to this, can use binding agent or adhesive, also can use the openly laminating method of exerting pressure.
In addition, preferably, after the lamination thin polyurethane rete, after approximately dry 1 minute, peel off the release paper that is adhered to the thin polyurethane rete in the air drier about 100 ℃.Be advisable through the maturation stage that enters next step after the hot air drying like this, directly in air drier, do not carry out ripening because do not carry out hot air drying, then because of polyurethane foam dressing shrinkage crimping, therefore the form that is difficult to roll up is twined, and is unfavorable for being retained in the moisture evaporation of polyurethane foam.If the inappropriate volatilization of moisture then can reduce exudate absorbing power and the infiltration rate of polyurethane foam dressing wound contact layer.Peel off the release paper that is adhered to the thin polyurethane rete after the hot air drying like this, then can obtain only to adhere at thin layer the polyurethane foam dressing of the present invention of release paper.Be adhered to the release paper of polyurethane foam, when the patient uses, peel off, and the face of removal release paper contacts in wound surface.
In an embodiment of the present invention, with 3, after the speed high-speed stirred polyurethane prepolymer and foaming mixture about 000rpm, the foaming mixed liquor is supplied on the fixing release paper that tilts at a certain angle, then it dropped down under the inclined plane approximately after 2 minutes, began to form the sticking colloidal polyurethane foam of tool.At this moment, moisture-permeability waterproof thin film and laminate surface (face of no-off paper) are contacted and directly carry out after the lamination, in 100 ℃ of air driers dry 3 minutes.
Ripening
Polyurethane foam dressing through above-mentioned lamination step preferably, also is included in the process of ripening in the air drier.
In an embodiment of the present invention, will be in above-mentioned steps through hot air drying and peel off the polyurethane foam dressing of the release paper that is adhered to thin layer, ripening certain hour in 50～70 ℃ air drier.If through the ripening of certain hour, then polyurethane material can shrink to a certain degree like this, and polyurethane outside thin layer can shrink in the lump and formed nature fold texture this moment.In addition, select the release paper such as AR-175 with wrinkle texture (Korean and Japanese volume company), also can obtain identical effect.In addition, also can improve the mechanical properties such as hot strength, percentage elongation by ripening.
The surface modification of polyurethane foam
The polyurethane foam that above-mentioned steps is made impregnated in after wetting agent and/or the drying, utilizes oxygen plasma to process, thereby increases the hydrophilic of polyurethane foam, improves infiltration rate.
Wetting agent separately or mix the uses such as two or more glycerol, vinegar essence, propylene glycol, sorbic acid, Polyethylene Glycol.When selecting glycerol, because the higher pretreating effect of glycerol concentration is better, therefore preferably, impregnated in the solution that mixes 5～20 weight portion glycerol in 100 weight portions, 50% ethanol water and carry out drying afterwards.Except ethanol, also can use methanol, isopropyl alcohol etc.But best for using ethanol.
Preferably, oxygen plasma is processed and is carried out about 10 seconds～2 minutes, is 30～60 seconds more.
Surface modification can only be selected an enforcement in wetting agent processing or the oxygen plasma processing, also can carry out oxygen plasma after carrying out the wetting agent processing and process, thereby carry out simultaneously two kinds of processing.For obtaining better effect, be preferably and carry out simultaneously two kinds of processing.Preferably, above-mentioned surface modification is in the end implemented in the step after foam dressing is finished in the above-mentioned steps preparation.But this is unrestricted, can after the preparation froth bed, implement at proper step as required.
In an embodiment of the present invention, polyurethane foam is fixed in after the test portion fixed station, utilizes rotary pump to form vacuum at inside reactor.By, utilize flow regulator to inject a certain amount of oxygen, conditioned reaction device internal pressure.Pressure fixing after 250mTorr, is injected approximately 10 minutes oxygen, approximately 30～60 seconds oxygen plasma occurs, to carry out the polyurethane foam surface treatment.
Figure 14 to Figure 16 is the curve chart of expression polyurethane foam dressing infiltration rate of the present invention.Shown in curve chart, with the increase in oxygen plasma processing time, the time that polyurethane foam dressing reaches the absorption saturation becomes shorter.In addition, impregnated in the wetting agent such as glycerol and dry after carry out that oxygen plasma processes, wetting agent is pretreated than not carrying out, it is shorter that it reaches the time that absorbs saturation.In addition, as shown in figure 16, process even do not carry out oxygen plasma, impregnated in the higher glycerite of concentration and carry out dryly, it is shorter that it reaches the time that absorbs saturation.
The structure of polyurethane foam dressing
By the polyurethane foam dressing of the present invention that the listing method is prepared from, have the froth bed and the thin polyurethane rete that are consisted of by the polyurethane foam foam, and that froth bed is divided into is two-layer.Below, by reference to the accompanying drawings polyurethane foam dressing structure of the present invention is described.
Fig. 1 to Fig. 4 is polyurethane foam dressing ideograph of the present invention.Fig. 1 is polyurethane foam dressing ideograph of the present invention, comprise the froth bed 10 and the waterproof polyurethane outside thin layer 20 that are consisted of by the polyurethane foam foam, and froth bed 10 has double-decker, namely being formed with diameter is the skin contacting adhesive layer 11 of the fine perforate of 1～50 μ m, and be formed with the intrinsic absorption layer 12 that diameter is a plurality of perforates of 1～1,000 μ m.In addition, perforate is specially the structure with a plurality of pores that connect perforate.The average diameter of pore is 1～50 μ m.
Fig. 2 removes after the bubble for polyurethane resin being utilized the vacuum stirring defoamer carry out deaeration, coats inferior light release paper 30B upper and carry out thin polyurethane rete 20 ideographs that drying is prepared from.At this moment, if polyurethane resin is selected the polyurethane resin that has both poisture-penetrability and water proofing property, even select as the used polyurethane resin of the preparation of above-mentioned polyurethane foam, import the polyurethane resin of hydrophilic group at main chain, then can obtain to have both the moisture-permeability waterproof based polyurethane thin layer of poisture-penetrability and water proofing property.
Fig. 3 is supplied to the release paper 30A through the silicon processing that tilts to fix by certain angle, polyurethane foam 10 ideographs that make it foam and be prepared from for after mixing polyurethane prepolymer and foaming mixture and the high-speed stirred when dropping down down.The mixed solution that froth bed mixes at prepolymer and foaming mixture directly is contacted with the face of silicon release paper 30A, be further divided into formation table (Skin) layer and two-layer 11,12 because of the stomata states difference self-assembling formation of face, and the face portion that contact with release paper 30A is than the trickleer pore of form of film (top layer) formation.Be formed with finer perforate, the face portion that contacts with release paper is referred to as wound surface contact layer 11, partly is referred to as absorbed layer 12 and form parts larger, more perforates.Absorbed layer is born main absorption function in polyurethane dressing of the present invention.
Fig. 4 is the polyurethane foam dressing ideograph that adheres to the state of release paper, and the release paper 30B that is attached to thin layer 20 is stripped from preparation process, and the release paper 30A that is attached to thin layer 10 will be thrown off in use.
In foam dressing of the present invention, wound surface contact layer 11 has the fine pores that diameter is 1～50 μ m, plays the effect that absorbs exudate, has the non-tack of wound surface.Intrinsic absorption layer 12 has a plurality of perforates that diameter is 1～1,000 μ m, can absorb to preserve 100～1,000 % by weight, has 0.1～0.8g/cm 3Density range.In addition, to have a plurality of average diameters that connect perforate be the structure of the pore of 1～50 μ m to above-mentioned pore again.Outside thin layer 20 is the moisture-permeability waterproof thin film, has 400～3,000g/m 2In the time of the high moisture permeability of/day (relative humidity 10～90%, 37 ℃, Desiccant Method), preventing the invasion of outside antibacterial and pathogenic bacteria, prevent that exudate from leaking to the outside, is that wound surface consists of moist environment.
Above-mentioned Fig. 1 to shown in Figure 4 be the example of polyurethane foam dressing of the present invention, and can prepare according to purposes and needs the dressing of the present invention of all size and form.
Below, the present invention is described in detail in conjunction with specific embodiments.But the present invention is not limited by following embodiment, and those of ordinary skill in the art can be without departing from the spirit and scope of the present invention, can make amendment, be out of shape the present invention or be equal to replacement.
Polyurethane prepolymer synthesis example (#1～3)
According to the condition shown in the table 1 and method synthesis of polyurethane prepolymer.
[table 1]
Figure G2008800211005D00181
From above-mentioned table 1 as can be known, add the cahin extension agent such as ethylene glycol or BDO or improve the year increase of the polyurethane prepolymer that synthesize with the content of hard segment.
Moisture-permeability waterproof based polyurethane synthesis example
According to the condition shown in the table 2 and the synthetic moisture-permeability waterproof based polyurethane resin of method.
[table 2]
Figure G2008800211005D00192
Moisture-permeability waterproof based polyurethane film preparation example
Moisture-permeability waterproof based polyurethane thin film technology is as follows: at first be prepared from moisture-permeability waterproof based polyurethane resin to 100 weight portions according to the method shown in the above-mentioned table 2, drop into 50 weight portion butanones, 15 weight portion dimethyl formamides, 5 weight portion pigment and stir preparation polyurethane mixed liquor.
With the polyurethane mixed liquor that is prepared from utilize coating thickness detector etc. by certain thickness coat inferior light release paper 30B (Youlchon chemical company) upper after, in 100 ℃ of air driers dry 30 minutes, thereby at the one side molding moisture-permeability waterproof based polyurethane thin film of inferior light release paper 30B.The thickness of the moisture-permeability waterproof based polyurethane thin film that is prepared from by said method is 20 μ m.
Foaming mixture preparation example (#1～3)
Prepare #1, #2, #3 foaming mixture according to the condition shown in the table 3.
[table 3]
Distinguish #1 #2 #3 Remarks
Deionized water (DIW) 2,000 2,000 2,000
Carboxymethyl cellulose 40 40 -
F-68 20 20 20 BASF AG
Glycerol - 100 - Cross-linking agent
Total preparation amount (g) 2,060 2,160 2,020
Polyurethane foam dressing preparation example (#1～21)
Being prepared as follows of polyurethane foam dressing: the foaming mixture that the polyurethane prepolymer that (1) is prepared from the above-mentioned synthesis example of 100 weight portions and 80 weight portions are prepared from above-mentioned foaming mixture preparation example, with 3,000rpm stirred after 10 seconds, be supplied to the silicon release paper A (Youlchol chemical company) that tilts to fix with the 45° angle degree, make the foaming mixed liquor along dropping down under the inclined plane.Employed prepolymer and foaming mixture and processing conditions are as shown in table 4 in each preparation example.
(2) foaming is dropped down approximately after 2 minutes under the mixed liquor, after the polyurethane foam of the sticking alternating state of tool reaches certain thickness, with the thin film of the 20 μ m thickness that are prepared from the moisture-permeability waterproof based polyurethane film preparation example, in the condition laminated that keeps certain interval.Then, be to adjust product thickness, in the situation that keep after certain interval presses down, in 100 ℃ of air driers dry 3 minutes.Polyurethane foam layer thickness and mechanical properties before the ripening are shown in chart 4.
(3) the dry inferior light release paper B that forms moisture-permeability waterproof based polyurethane thin film that peels off afterwards, then ripening 24 hours in 70 ℃ air drier, the thickness of the polyurethane dressing that is prepared from like this and the thickness of outside thin layer and the mechanical properties after the ripening, as shown in table 4.
Oxygen plasma is processed example
(Model EPPS 2000 PLASMARTInc.), on the surface of the prepared polyurethane foam dressing of above-mentioned preparation example, respectively carries out 30 seconds, 60 seconds processing to utilize the oxygen plasma reaction unit.The pressure fixing of this moment is 250mTorr, and (Model 801, Varian) measure, and the flow of institute's inflow gas controlled with mass flow controller (MFC, Brooks, Japan, Model 5850E) with vacuometer for the pressure of inside reactor.The isoionic color development light of inside reactor that utilizes is determined its stability.The oxygen plasma processing time of each preparation example, as shown in table 4.
Wetting agent is processed example
The glycerol that mixes 5 weight portions, 10 weight portions and 20 weight portions in 100 weight portions, 50% ethanol water, the mixed solution that the preparation glycerol concentration is different also will be after the upper polyurethane foam dressing dipping prepared to preparation example 1 minute, and drying is 24 hours in 80 ℃ vacuum drier.The handled glycerol concentration of each preparation example, as shown in table 4.
Figure G2008800211005D00231
Figure G2008800211005D00241
Test example
Utilize method as described below to measure the polyurethane foam dressing physical property of the prepared polyurethane foam dressing of above-mentioned preparation example and following comparative example, and the result who measures is as shown in table 5.In addition, utilize scanning electron-microscopic observation polyurethane foam dressing of the present invention and commercial polyurethane foam dressing internal structure, and diagram 5 is to Figure 13.The infiltration rate of the polyurethane foam dressing that finally is prepared from addition, such as the curve chart of Figure 14 to 16.
1. mechanical properties (hot strength, percentage elongation)
For recording the not mechanical properties of the polyurethane foam of lamination moisture-permeability waterproof based polyurethane outside thin layer, utilize universal testing machine (Universial Test Machine, Instron), with pressure transducer (Load Cell) 50N, mark wide 20mm, gauge length (Gauge Length) 30mm, test speed (Cross Head Speed) 100mm/min measures.
2. absorb saturated velocity (second)
Get placed 24 hours in the dressing room temperature of 3cm * 3cm size after, dipping is stored in 37 ℃ the distilled water and records the time that no longer occurs till the weight change.
3. moisture permeability
Utilize constant temperature and humidity instrument (SAMHEUNG INSTRUMENT, SH-CTH 150) to measure according to ASTM E 96-94 (Desiccant Method), this moment, the temperature of constant temperature and humidity instrument was 37 ± 2 ℃, and relative humidity is 80 ± 5%.
4. form
Utilize sweep electron microscope to record the perforate of polyurethane dressing of the present invention and shape and the thin layer thickness of pore.
Comparative example 1
For physical property compares, the Carefoam of Saeron drugmaker is selected in test TMPhysical property utilizes the described method of above-mentioned preparation example to measure, and its result is as shown in table 5.
Comparative example 2
For physical property compares, Smith﹠amp is selected in test; The Allevyn of Nephew company TMPhysical property utilizes the described method of above-mentioned preparation example to measure, and its result is as shown in table 5.
[table 5]
Figure G2008800211005D00271
*Existing product: under the state that outside thin layer is arranged, measure hot strength and percentage elongation.
Shown in table 5 and Figure 14 to 16, under the same conditions, more carry out oxygen plasma and process, reach the time that absorbs saturation shorter.Reaching the time that absorbs saturation shortens, and the time that means quick absorption exudate and preserve to greatest extent exudate shortens.The trap balancing speed of the preparation example 7 of processing without wetting agent and oxygen plasma is 115sec, but the preparation example 8 of carrying out oxygen plasma processing in 30 seconds shortens to 85sec, speed slightly is improved, and the preparation example 9 of carrying out processing in 60 seconds shortens to 70sec, and speed is improved again.In addition, than preparation example 8, the preparation example 9 only processed through oxygen plasma, carry out carrying out again preparation example 11, the preparation example 12 that oxygen plasma is processed after the moistening processing with mixing the solution that 100 weight portions, 50% ethanol water and 5 weight portion glycerol are prepared from first, its absorb saturation time shorten to 70 seconds, 60 seconds.In addition, preparation example 13, preparation example 14 expressions are not carried out oxygen plasma and are processed, and only need to improve humectant content dipping and the dry pretreatment such as glycerol, can shorten the time that absorbs saturation that reaches yet.Therefore, dipping that can be by regulating oxygen plasma processing time and wetting agent whether, speed etc., regulate the time that absorbs saturation that reaches.
In addition, shown in preparation example 1～7, when the synthesis of polyurethane prepolymer, if add the cahin extension agents such as ethylene glycol or BDO, then with the increase of hard segment content, can improve mechanical properties, but increase to a certain extent the speed that absorbs saturation that reaches.In addition, if interpolation as three alcoholic compounds such as glycerol of cross-linking agent, then because increasing the degree of cross linking, can improve mechanical properties.Therefore, can whether exist by hard segment content and cross-linking agent and regulate mechanical properties.
Shown in preparation example 15, preparation example 16 and preparation example 17, minimizing with the thickness adjusting play, the size of perforate is more and more less, and the pore that connects perforate reduces thereupon, absorb saturated velocity thereby reduce, but shown in preparation example 18, preparation example 19 and preparation example 20, can process or wetting agent pretreatment improvement absorption saturated velocity by oxygen plasma.In addition, with the minimizing of thickness adjusting play, the size of whole perforate and pore diminishes and improves foam density, therefore can increase to a certain extent mechanical properties.
In addition, shown in preparation example 1, preparation example 3, under the same conditions, in foaming mixture, add carboxymethyl cellulose, than not adding carboxymethyl cellulose, can increase its mechanical properties.
Therefore, can pass through the content of cahin extension agent, hard segment, whether the interpolation of cross-linking agent, the powder additives such as carboxymethyl cellulose, the gap of thickness adjustment part, regulate the mechanical properties of prepared polyurethane foam dressing etc., and by oxygen plasma processing or wetting agent processing etc., the polyurethane foam dressing that preparation has various physical property and characteristics.
Fig. 5 to Fig. 8 is the sweep electron microscope photo of polyurethane foam dressing of the present invention, and wherein, Fig. 5 is the photo of preparation example 15, and Fig. 6 is the photo of preparation example 16, and Fig. 7 is the photo of preparation example 17, and Fig. 8 is the photo of preparation example 21.In the photo, A is intrinsic absorption layer 12 photos, and B is wound surface contact layer 11 photos.As can be known, than the wound surface contact layer, absorbed layer has large and many perforate and connects the pore (Pore) of perforate from photo.In addition, the thickness adjusted gap is fewer, and the perforate size of absorbed layer is less, and the top layer of wound surface contact layer increases, and hole shape becomes ellipse from circle, and the pore that connects perforate reduces.Such structure is unfavorable for the absorption of exudate, absorbs saturated velocity but can increase by surface modifications such as wetting agent pretreatment or oxygen plasma processing, does not therefore become problem.
Fig. 9 is the Medifoam-N of Ildong drugmaker as commercial polyurethane foam dressing TMSweep electron microscope photo (LOT.01N22506 produces day: 060207, Republic of Korea).Intrinsic absorption layer " A " is made of even fine open-celled structure.And wound surface contact layer " B " is more without the top layer S of perforate, and than other products, the size of perforate is also very little, and therefore difference is very obvious.
Figure 10 is the Medifoam-F of Ildong drugmaker as commercial polyurethane foam dressing TMSweep electron microscope photo ((LOT.02F01007 produces day: 070405, Republic of Korea).At this moment utilize mould to prepare after the bulk product, utilize horizontal guillotine to remove the product on top layer.Intrinsic absorption layer and wound surface contact layer all have the structure of same form.If but the perforate of wound surface contact layer is too much or excessive like this, though then improve greatly the exudate infiltration rate because getting perforate with contacted of skin, but be combined with the skin histology that wound site is newly-generated, therefore when skin is removed dressing, cause pain or secondary damage.
Figure 11 is the Smith﹠amp as commercial polyurethane foam dressing; The Allevyn of Nephew company TMSweep electron microscope photo (LOT.0611 60229, produce day: 060313, Britain).The same with other products, consisted of by perforate and the pore that connects perforate, and perforate is slightly large.And, the top layer S of wound surface contact layer " B " cambium layer pressure network shaped polymer thin film.
Figure 12 is the Carefoam as the Saeron drugmaker of commercial polyurethane foam dressing TMSweep electron microscope photo (LOT.C05002 produces day: 051222, Republic of Korea).Seem and have as shown in figure 10 form, but than Figure 10, the size and shape of its perforate is irregular.Meanwhile, the perforate of wound surface contact layer is combined with the skin histology that wound site is newly-generated greatly and very many, therefore causes pain or secondary damage when skin is removed dressing.
Figure 13 is the Biatain as the Coloplast company of commercial polyurethane foam dressing TMSweep electron microscope photo (LOT.743794 produces day: 2006.3, Denmark).Intrinsic absorption layer have with such as the similar open-celled structure of the product of Fig. 8.Just, the wound surface contact layer is the form that comprises a plurality of perforates of some top layer S.
As mentioned above, the polyurethane foam dressing that forms produced according to the present invention than existing other products, has very various form, can be according to various wound states and condition, and directional preparation has the polyurethane foam dressing of suitable infiltration rate and structure.In addition, can carry out as required the surface modification treatment such as wetting agent pretreatment, oxygen plasma processing, to regulate the hydrophilic of polyurethane foam dressing.
Industrial applicibility
The invention provides a kind of new polyurethane foam dressing preparation method, its mixed at high speed hydrophilic polyurethane prepolymers, deionized water, after the preparation such as surfactant and the cross-linking agent foaming mixed liquor, this foaming mixed liquor is spued fixing on the release paper that silicon is processed to tilting by certain angle, the mixed liquor that then foams foams when dropping down under the inclined plane, then, at the sticking colloidal lamination of tool moisture-permeability waterproof based polyurethane thin layer, and the certain interval of being separated by before sclerosis is to adjust thickness, thereby significantly improve productivity and the working (machining) efficiency of foam dressing, not limited by pot life, therefore can produce in a large number foam dressing, significantly reduce production costs the foam dressing that expense preparation that can be cheap has outstanding physical property.
In addition, the prepared polyurethane foam that forms is utilized after wetting agent dipping and the drying, utilize oxygen plasma to process to improve infiltration rate, thereby the polyurethane foam dressing that the preparation function is strengthened, meanwhile, processing time by oxygen plasma and the dipping of wetting agent whether, the surface modification condition such as concentration, regulate the absorption saturation time of foam dressing, can be according to various wound states and condition, directional preparation has the polyurethane foam dressing of suitable infiltration rate and structure.
The present invention can provide the new polyurethane foam dressing, and it significantly improves the productive while of foam dressing by novel and high efficiency technique, and its physical property is more outstanding than existing methodical high price foam dressing, and easily with all size and shape molding.
Reference numeral
10: the froth bed that forms perforate
11: wound surface contact layer 12: intrinsic absorption layer
P: pore (pore) O: perforate
20: anapsid water proofing property outside thin layer F: outside thin layer
S: top layer 30A, 30B: release paper
D: the angle of inclination 40 of release paper: foaming mixed liquor supply department.

Claims (14)

1. polyurethane foam dressing preparation method, comprise: (a) step of preparation anapsid waterproof polyurethane thin layer, after 100 weight portion polyurethane resins add 20～70 weight portion methyl ethyl ketones and the mixing of 5～30 weight portion dimethyl formamides, remove bubble, coat release paper and dry;
(b) step of polyurethane preformed polymer drops into isocyanates and reacts to the mixed solution that comprises polyhydric alcohol and antioxidant;
(c) step of preparation foaming synthetic is mixed 60～120 parts by weight of deionized water, 0.5～40 weight portion cross-linking agent and 1～10 weight portion surfactant as foaming agent;
(d) step of preparation foaming mixed liquor, to the polyurethane prepolymer that 100 weight portions are prepared from by above-mentioned (b) step, the foaming synthetic that mixed at high speed 50～150 weight portions are prepared from by above-mentioned (c) step;
(e) step of preparation polyurethane foam, to be supplied to by the foaming mixed liquor that above-mentioned (d) step is prepared from the release paper of fixing with the angle inclination of 30～70 degree, it is foamed when dropping down under the inclined plane, to obtain 1～20mm thickness, has the colloidal polyurethane foam of the viscosity before the sclerosis;
(f) adjust the step of foam dressing thickness, the polyurethane foam that lamination is prepared from by above-mentioned (e) step and the anapsid waterproof polyurethane thin layer that is prepared from by (a) step, and the certain interval of being separated by pushes.
2. a kind of polyurethane foam dressing preparation method according to claim 1, wherein said polyhydric alcohol is dihydroxylic alcohols.
3. a kind of polyurethane foam dressing preparation method according to claim 1 is characterized in that: in above-mentioned (f) step, carry out hot air drying after lamination polyurethane foam and thin polyurethane rete.
4. a kind of polyurethane foam dressing preparation method according to claim 1 is characterized in that: after above-mentioned (f) step, also be included in the step of in the air drier polyurethane foam dressing being carried out ripening.
5. a kind of polyurethane foam dressing preparation method according to claim 1, it is characterized in that: above-mentioned foaming mixed liquor also comprises 0.01～20 weight portion medicine.
6. a kind of polyurethane foam dressing preparation method according to claim 1 is characterized in that: above-mentioned foaming mixed liquor comprises that also 0.01～20 weight portion absorbs adjuvant and wetting agent.
7. according to claim 1 to 6 described any polyurethane foam dressing preparation methods, it is characterized in that: also comprise above-mentioned polyurethane foam be impregnated in wetting agent and carries out drying, thus the step of raising froth bed infiltration rate.
8. a kind of polyurethane foam dressing preparation method according to claim 7 is characterized in that: also comprise above-mentioned impregnated in after wetting agent and the drying, carry out the step that oxygen plasma is processed.
9. a kind of polyurethane foam dressing preparation method according to claim 7 is characterized in that: above-mentioned wetting agent select in glycerol, vinegar essence, propylene glycol, sorbic acid and the Polyethylene Glycol more than a kind.
10. according to claim 1 to 6 described any polyurethane foam dressing preparation methods, it is characterized in that: comprise that also above-mentioned polyurethane foam is carried out oxygen plasma to be processed, thereby improve the step of froth bed infiltration rate.
11. according to claim 1 to 6 described any polyurethane foam dressing preparation methods, it is characterized in that: above-mentioned polyhydric alcohol is for having 2 above hydroxyls, molecular weight be 500～6,000 and ethylene oxide content be 20～90% ethylene oxide/propylene oxide copolymer.
12. according to claim 1 to 6 described any polyurethane foam dressing preparation methods, it is characterized in that: above-mentioned isocyanates is selected isophorone vulcabond, 2,4-toluene di-isocyanate(TDI), 2, in 6-toluene di-isocyanate(TDI) and the methylene diphenyl isocyanate more than a kind.
13. a kind of polyurethane foam dressing preparation method according to claim 2 is characterized in that: above-mentioned dihydroxylic alcohols select in ethylene glycol, propylene glycol, 1,3 butylene glycol, BDO and 1, the 6-hexanediol more than a kind.
14. a kind of polyurethane foam dressing preparation method according to claim 8 is characterized in that: above-mentioned wetting agent select in glycerol, vinegar essence, propylene glycol, sorbic acid and the Polyethylene Glycol more than a kind.
CN2008800211005A 2007-06-21 2008-06-17 Method for producing hydrophilic foam dressing Active CN101730515B (en)

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KR1020080018998A KR100937816B1 (en) 2007-06-21 2008-02-29 A Method for Manufacturing Hydrophilic Wound Dressing and the Hydrophilic Wound Dressing
KR10-2008-0018998 2008-02-29
PCT/KR2008/003414 WO2008156285A1 (en) 2007-06-21 2008-06-17 Method for producing hydrophilic foam dressing and hydrophilic foam dressing produced thereby

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