The specific embodiment
In this manual, " hydrophilic polyurethane " is meant because of importing hydrophilic group and has more hydrophilic polyurethane than general polyurethane.In addition, in the present invention, " poisture-penetrability thin film " be meant because of the hydrophilic polyurethane that will import hydrophilic group as raw material, general polyurethane film has more the polyurethane film of poisture-penetrability.In addition, in this manual, " moisture-permeability waterproof thin film " be meant 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; The colloidal polyurethane foam and the thin polyurethane rete of property that lamination has sticking (Tack) also adjusted the step of foam dressing thickness; Increase the 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 vacuum stirring deaeration machine 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 for use, even select for use as the used polyurethane resin of the preparation of above-mentioned polyurethane foam, at the polyurethane resin of main chain importing hydrophilic group, 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, till the theoretical value that reaches NCO content (%), react.
Above-mentioned polyhydric alcohol can separately or mix two or more following substances to be used: 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 carbonic ester glycol, 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 is published.Therefore, best selecting for use 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 use.For example, can separately or mix two or more following substances uses: as 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, 1,5-naphthalene diisocyanate, tolidine vulcabond, hexa-methylene-1,6-vulcabond (Hexamethylene-1,6-diisocyanate), isophorone vulcabond, XDI, cyclohexane extraction-1, the 4-vulcabond (Cyclohexylene-1,4-diisocyanate), lysinediisocyanate, tetramethylene-XDI etc.Preferably, select isophorone vulcabond, 2,4 toluene diisocyanate, 2 for use, 6-toluene di-isocyanate(TDI) and methylenediphenyl diisocyanates etc.
Above-mentioned diatomic alcohol compounds is independent or mix two or more following substances uses: 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 1, the 4-butanediol uses.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.But if 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 mixing stirring polyurethane prepolymer and foaming synthetic, being supplied on the inclination release paper, because of the not good enough not easy-formation of flowability.Otherwise, then too fast if viscosity is low excessively because of on the 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 be regulated above-mentioned viscosity easily according to situations such as foaming mixture viscosity and forming temperatures.
In addition, when preparation polyurethane prepolymer of the present invention, also can pass through the disclosed additive of disclosed method interpolation.Especially comprise antioxidant in these additives.Above-mentioned antioxidant is separately or mix two or more following substances and use it: 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 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 weight % of whole polyurethane prepolymers.
The preparation of foaming mixture
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 0.01~2 weight portion pigment, 0.01~20 weight portion medicine, 0.1~40 weight portion wetting agent as required and absorb adjuvant.
Cross-linking agent can separately or mix two or more glycerol, trimethylolpropane, 1,2, uses such as 4-butantriol, sorbic acid.Cross-linking agent improves the effect of foam mechanical rerum natura by cross-linking reaction when polyurethane foam molding.
Surfactant can be by openly purposes and method are used disclosed 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 to clean a wound under the situation that does not injure tissue 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 disclosed 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, the L-aspartic acid, the L-NaAsp, the DL-alanine, the L-isoleucine, cetirizine hydrochloride, glycine, glycerol, L-glutaminate, L-glutamic acid, the L-sodium glutamate, pyrimidine acid (Pyridine acid), the L-threonine, sericin, serine, L-tyrosine, heparin, sodium chondroitin sulfate, sodium alginate, gelatin etc. can be contained in the above-mentioned foaming mixed liquor according to disclosed 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.Just play the effect of filler, and filler is meant that interpolation improves the material of intensity and weight etc. with anti-aging in the practicability process of rubber or plastics.For example, on carbamide formalin resin or carbolic acid formalin resin or synthetic leather, during the molded polyurethanes thin film, obtain enough intensity, therefore add fiber, asbestos, wood powder etc. and resin that the processing machinery rerum natura is strengthened because of not depending merely on resin.
In the present invention, " medicine " comprises disclosed medicine and the antibacterial that wound is had curative effect, 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 disclosed capacity and method, in above-mentioned scope separately or mix two or more being contained in the said mixture.
In addition, be infection and the propagation that prevents various pathogenic bacterias, can comprise disclosed 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 in above-mentioned scope, be contained in the said mixture according to disclosed capacity and method.
In addition, can disclosed other medicines be contained in the dressing of the present invention according to the purpose of treatment and prevention.
In addition, in order to increase the absorbability of polyurethane foam, in said mixture, can in above-mentioned scope, comprise absorption adjuvant such as disclosed high-absorbable macromolecule.
In addition, in foaming mixture of the present invention, add disclosed additives such as stabilizing agent, preservative agent, rerum natura regulator on a small quantity 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 the fixed release paper 30A that tilts by certain angle.The foaming mixed liquor of being supplied 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, and it is fixing to keep the angle of 30~70 degree to tilt.If the angle of inclination of release paper is below 30 degree, because of the foaming mixed liquor is difficult for dropping down down, therefore easy-formation not, and if more than 70 degree, then too fast along dropping down under the inclined plane, so also easy-formation not because of the foaming mixed liquor.In the present invention,, therefore not limited by pot life because of the mixed liquor that will foam by above-mentioned inclined plane is supplied on the release paper, but the certain thickness product of continuous production.Figure 17 goes up the state diagram of supply foaming mixed liquor to the fixed release paper 30A that tilts by certain angle d for expression.
The froth bed of above-mentioned molding preferably, during the colloidal state of the viscosity before having sclerosis, carries out next step lamination operation.Promptly, on release paper,, directly carry out the lamination with the thin polyurethane rete, need not to use other independent technologies of binding agent or adhesive etc. like this with after the state forming polyurethane foam with heavy-gravity viscosity as colloid, can finish lamination simply, to improve process efficiency.
Preferably, release paper is in this step selected macromolecule membrane or the stationery release paper of handling through silicon face for use.
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 the 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 thereto, and 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 about 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.As if the inappropriate volatilization of moisture, then can reduce the 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 to the polyurethane foam dressing of the present invention of release paper at thin layer.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 mixed liquor that will foam is supplied on the fixed release paper that tilts at a certain angle, after then it dropped down about 2 minutes, begin to form colloidal polyurethane foam with viscosity under the inclined plane.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 release paper such as AR-175 with wrinkle texture (Korean and Japanese volume company) for use, also can obtain identical effect.In addition, also can improve 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 handle, thereby increases the hydrophilic of polyurethane foam, improves infiltration rate.
Wetting agent separately or mix uses such as two or more glycerol, vinegar essence, propylene glycol, sorbic acid, Polyethylene Glycol.When selecting glycerol for use,, 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 because of the high more pretreating effect of glycerol concentration is good more.Except that ethanol, also can use methanol, isopropyl alcohol etc.But it is best for using ethanol.
Preferably, oxygen plasma is handled 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 handle, thereby carry out two kinds of processing simultaneously.For obtaining better effect, be preferably and carry out two kinds of processing simultaneously.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 implement at proper step as required after the preparation froth bed.
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 about 10 minutes oxygen, about 30~60 seconds oxygen plasma takes place, 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 short more.In addition, impregnated in wetting agent such as glycerol and dry after carry out that oxygen plasma handles, wetting agent is pretreated than not carrying out, it is short more that it reaches the time that absorbs saturation.In addition, as shown in figure 16, handle even do not carry out oxygen plasma, impregnated in the high more glycerite of concentration and carry out exsiccantly, it is short more 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 constitute by the polyurethane foam foam, and that froth bed is divided into is two-layer.Below, in conjunction with the accompanying drawings polyurethane foam dressing structure of the present invention is described.
Fig. 1 to Fig. 4 is a polyurethane foam dressing ideograph of the present invention.Fig. 1 is a polyurethane foam dressing ideograph of the present invention, comprise the froth bed 10 and the waterproof polyurethane outside thin layer 20 that constitute by the polyurethane foam foam, and froth bed 10 has double-decker, promptly 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 vacuum stirring deaeration machine carry out deaeration, coats inferior light release paper 30B and goes up 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 for use, even select for use as the used polyurethane resin of the preparation of above-mentioned polyurethane foam, at the polyurethane resin of main chain importing hydrophilic group, 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 by the fixed release paper 30A that handles through silicon of certain angle inclination, polyurethane foam 10 ideographs that foam when its infra is dropped down and be prepared from for after mixing polyurethane prepolymer and foaming mixture and the high-speed stirred.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 because of the stomata states difference of face form naturally two-layer 11,12, and the face portion that contacts 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 bigger, 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 weight %, has 0.1~0.8g/cm
3Density range.In addition, to have a plurality of average diameters that connect perforate again be the structure of the pore of 1~50 μ m to above-mentioned pore.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 constitutes 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 the dressing of the present invention of all size and form according to purposes and needs.
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 condition shown in the table 1 and method synthesis of polyurethane prepolymer.
[table 1]
From above-mentioned table 1 as can be known, add ethylene glycol or 1, cahin extension agent such as 4-butanediol or improve the year increase of the synthetic polyurethane prepolymer of institute with the content of hard segment.
Moisture-permeability waterproof based polyurethane synthesis example
According to condition shown in the table 2 and the synthetic moisture-permeability waterproof based polyurethane resin of method.
[table 2]
Moisture-permeability waterproof based polyurethane film preparation example
Being prepared as follows of moisture-permeability waterproof based polyurethane thin film: at first be prepared from moisture-permeability waterproof based polyurethane resin according to the method shown in the above-mentioned table 2 to 100 weight portions, drop into 50 weight portion butanones, 15 weight portion dimethyl formamides, 5 weight portion pigment and stir preparation polyurethane mixed liquor.
Utilize coating thickness detector etc. to coat after inferior light release paper 30B (Youlchon chemical company) goes up the polyurethane mixed liquor that is prepared from by certain thickness, 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 forms by method for preparing 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 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 45 degree fixed silicon release paper A (Youlchol chemical company) that tilts, 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) make in a manner described after foaming dropped down about 2 minutes under the mixed liquor, after the polyurethane foam of the alternating state with viscosity 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, for adjusting product thickness, after pressing down under the situation that keeps certain interval, drying is 3 minutes in 100 ℃ of air driers.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 handled 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 handled 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 has nothing in common with each other also will be after the last 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.
The test example
Utilize method as described below to measure the polyurethane foam dressing rerum natura of 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 diagrammatic sketch 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 of no longer taking place 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 the shape and the thin layer thickness of pore.
Comparative example 1
For rerum natura compares, the Carefoam of Saeron drugmaker is selected in test for use
TMRerum natura utilizes the described method of above-mentioned preparation example to measure, and its result is as shown in table 5.
Comparative example 2
For rerum natura compares, Smith﹠amp is selected in test for use; The Allevyn of Nephew company
TMRerum natura utilizes the described method of above-mentioned preparation example to measure, and its result is as shown in table 5.
[table 5]
*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, carry out oxygen plasma more and handle, it is short more to reach the time that absorbs saturation.Reaching the time that absorbs saturation shortens, and the time that means the fast Absorption exudate and preserve exudate to greatest extent shortens.The trap balancing speed of the preparation example of handling without wetting agent and oxygen plasma 7 is 115sec, but the preparation example 8 of carrying out oxygen plasma processing in 30 seconds shortens to 85sec, speed slightly improves, and the preparation example 9 of carrying out handling in 60 seconds shortens to 70sec, and speed is improved again.In addition, than preparation example 8, the preparation example 9 only handled through oxygen plasma, earlier carry out carrying out preparation example 11, the preparation example 12 that oxygen plasma is handled again after the moistening processing with mixing the solution that 100 weight portions, 50% ethanol water and 5 weight portion glycerol are prepared from, its absorption saturation time shortens to 70 seconds, 60 seconds.In addition, preparation example 13, preparation example 14 expressions are not carried out oxygen plasma and are handled, and only need to improve humectant content dipping and exsiccant 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 ethylene glycol or 1, cahin extension agents such as 4-butanediol then with the increase of hard segment content, can improve mechanical properties, but increase the speed that absorbs saturation that reaches to a certain extent.In addition, if interpolation as three alcoholic compounds such as glycerol of cross-linking agent, then because of 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 littler, 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 handle 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 mechanical properties to a certain extent.
In addition, shown in preparation example 1, preparation example 3, under the same conditions, in foaming mixture, add carboxymethyl cellulose,, can increase its mechanical properties than not adding carboxymethyl cellulose.
Therefore, can pass through the content of cahin extension agent, hard segment, whether the interpolation of cross-linking agent, 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 rerum naturas 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 big and many perforate and connects the pore (Pore) of perforate from photo.In addition, the thickness adjusted gap is few more, and the perforate size of absorbed layer is more little, 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 ", the top layer S of no perforate is more, 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.But if the perforate of wound surface contact layer is too much or excessive like this, though then improve the exudate infiltration rate greatly because of getting perforate with contacted of skin, but the skin histology newly-generated with wound location combines, and therefore causes pain or secondary damage when skin is removed dressing.
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, constitute by perforate and the pore that connects perforate, and perforate is big slightly.And wound surface contact layer " B " forms the top layer S of lamination network polymers 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 form as shown in figure 10, but than Figure 10, the size of its perforate and out-of-shape.Meanwhile, the perforate of wound surface contact layer greatly and very many, the skin histology newly-generated with wound location combines, and 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 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 the infiltration rate that it is suitable that beam system is got everything ready and the polyurethane foam dressing of structure.In addition, can carry out surface modification treatment such as wetting agent pretreatment, oxygen plasma processing as required, to regulate the hydrophilic of polyurethane foam dressing.