Background technology
Skin has the invasion of the outer pathogenetic bacteria of opposed body, drains human body waste, prevents that the body water evaporation is lost, regulates human body temperature, experiences the important function such as stimulation of pressure, cold, temperature.Because of wound, scratch, burn and fester etc. when causing skin damage, be easy to bacterial infection, or fluid loss take place and cause various complication, need use medical dressing to protect wound surface when therefore treating and promote wound healing.Traditional medical dressing (gauze) only works to cover wound surface, and along with developing rapidly of progress, particularly modern medicine, biology and the polymer material science of the development of society and science and technology, basic variation has taken place the notion of modern dressing.Modern medical dressing should possess: the spreadability that (1) is excellent can stop the breeding on wound of bacterial invasion and restricting bacterial; (2) good moisture pick-up properties and blocking performance can absorb wound fluid, hinders the dipping of transudate to health tissues simultaneously; (3) better elastic, pliability, breathability and hemostatic function; (4) good biocompatibility, life-time service can not cause ill symptomses such as wound location skin sensitivity or anaphylaxis; (5) provide moist healing environment, the healing of accelerated in wounds; (6) stable on wound surface, easily remove, it is convenient to use and store; (7) biodegradable, its garbage can not cause environmental pollution.The calcium alginate fibre non-woven fabric medical dressing is one of modern medical dressing of present extensive use, can satisfy the requirement of above-mentioned modern medical dressing.This medical dressing is raw material with the calcium alginate fibre, processes by the needle punched non-woven fabrics means, but exists the long and cost of work flow than problems such as height, has limited the use in enormous quantities of this kind dressing.
Sponge material has very strong water absorbing capacity because of having special loose structure, when contacting with the wound of humidity, wound fluids such as pus and blood are absorbed among the sponge by pore, and by inside and the back back side transfer of contact surface, thereby played the effect that pus and blood is removed from wound surface to sponge.Simultaneously, the transudate that is adsorbed in the sponge material is not volatile, and the wet environment that provides wound healing to need quickens the growth of wound surface granulation tissue, so sponge material is suitable for making medical dressing very much, and technological process is shorter, and cost is lower.Freeze-drying is a kind of simple effective method of preparation sponge material, has been widely used in preparing the sponge medical dressing at present.The Chinese patent publication number is CN 1380109A, open day is on November 20th, 2002, denomination of invention is chitosan, collagen and calcium alginate compounded spongy biological dressing and preparation technology thereof, it is raw material that this application case discloses with chitosan, collagen and calcium alginate, prepares the method for sponge dressing by freeze-drying method.The Chinese patent publication number is CN 1416907A, open day is on May 14th, 2003, denomination of invention is medical collagen sponge and preparation method thereof, it is raw material with collagen that this application case discloses a kind of, it is better with repairing effect that the employing freeze-drying prepares the wound surface hemostasis, the method for the medical collagen sponge that price is low.The Chinese patent publication number is CN 1425471A, open day is on June 25th, 2003, denomination of invention is wound healing sponge medical dressing of a kind of biological compound prescription and preparation method thereof, it is raw material that this application case discloses with chitosan, collagen and glycerol, prepares the method for sponge medical dressing by freeze-drying method.The Chinese patent publication number is CN 101301487A, open day is on November 12nd, 2008, denomination of invention is a kind of gelatin/bioactivity glass composite sponge dressing and preparation method thereof, it is raw material that this application case discloses with gelatin and bioactive glass powder, adopts freeze-drying to prepare the method for double-deck soft sponge dressing.The Chinese patent publication number is CN 101954115A, open day is on January 26th, 2011, denomination of invention is antibacterial medical sponge dressing and preparation method thereof, it is raw material that this application case discloses with polyvinyl alcohol, nanometer silver, fibroin albumen, is equipped with the method for antibacterial medical sponge dressing by the cool-drying legal system.
Adopt the Freeze Drying Technique of bibliographical information, the technology of preparation calcium alginate sponge is: preparation sodium alginate soln → template casting → low temperature pre-freeze → lyophilization → calcium chloride water is crosslinked → and washing → lyophilization → calcium alginate sponge.(preparation research of calcium alginate porous support, functional material, 1703-1708) adopt above-mentioned prepared to go out the calcium alginate porous support of pore diameter range between 100~300 μ m at 2009 the 10th phases to people such as Hao Xiaoli.The method needs secondary freezing, and complex process and energy consumption height, and the compact structure of the calcium alginate sponge that obtains, hard and lack flexibility only are suitable as tissue engineering bracket, are difficult to be applied to medical dressing field.In addition, people such as Hao Xiaoli (preparation of two kinds of calcium alginate films and water absorbing properties, polymer material science and engineering, 2010 the 4th phases, 143-145) report, adopt the primary freeze drying technology, obtained the calcium alginate sponge, though reduce energy consumption and simplified technology, finer and close more than the sponge structure that secondary freeze drying technology makes, elasticity and pliability are poorer, the more difficult medical dressing field that is used for.
Summary of the invention
Problem at above-mentioned existence, the object of the present invention is to provide a kind of various types of skin traumas such as surgical wound, empyrosis wound surface that are used for the treatment of, and pliability, hygroscopicity and elasticity excellence, production technology is simple, calcium alginate sponge medical dressing that cost is low and preparation method thereof, to achieve these goals, its technical solution is:
A kind of calcium alginate sponge medical dressing, calcium alginate sponge medical dressing is by two kinds of sodium alginate blend solutions that molecular weight is different, be shaped through lyophilization, calcium ion crosslinking curing and softening agent are handled and are formed, and wherein the quality percentage composition of each component is respectively in the calcium alginate sponge medical dressing:
Low molecular weight seaweed acid sodium 70%~90%
High molecular sodium alginate 8%~25%
Softening agent 2%~5%
Wherein, the number-average molecular weight of low molecular weight seaweed acid sodium raw materials is 10000~50000, and the number-average molecular weight of high molecular sodium alginate raw material is 300000~500000, and softening agent is a kind of in Polyethylene Glycol or glycerol or 1,3 butylene glycol or the amido silicon oil.
A kind of preparation method of calcium alginate sponge medical dressing, the preparation method of calcium alginate sponge medical dressing comprises the steps:
The preparation of a sodium alginate blend solution
Take by weighing low-molecular-weight sodium alginate according to 4.2%~5.4% of distilled water quality, and it is even to add in the distilled water it to stirring and dissolving, obtain the solution of low molecular weight seaweed acid sodium, take by weighing high-molecular weight sodium alginate according to 0.6%~1.8% of distilled water quality then, add in the above-mentioned solution, stirring at room is even to dissolving, obtains the sodium alginate blend solution.
The preparation of b sodium alginate sponge
The sodium alginate blend solution that step a is made places the cryogenic thermostat device, mechanical agitation limit, limit makes the solution cooling, treat that solution is cooled to 0 ℃~5 ℃ and stops to stir, divide and install in the mould, mould is positioned over pre-freeze in the ultra cold storage freezer, the pre-freeze temperature is-80 ℃~-10 ℃, the pre-freeze time is 1~5h, after pre-freeze is finished mould is placed freezer dryer, baking temperature is-50 ℃~-20 ℃, vacuum is below the 20Pa, and the processing time is 6~36h, the sodium alginate sponge that the dry back demoulding obtains being shaped.
The preparation of c calcium alginate sponge
Take by weighing softening agent according to 2%~5% of ethanol quality, the softening agent that takes by weighing is added in the ethanol, be stirred to mix homogeneously, obtain the mixed solution of ethanol and softening agent, take by weighing calcium chloride according to 3%~6% of ethanol quality then, add the calcium chloride that takes by weighing in above-mentioned mixed solution stirring and dissolving, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge that step b is obtained is immersed in and carries out crosslinking curing in the above-mentioned coagulating bath, the crosslinking curing temperature is 25 ℃~40 ℃, the crosslinking curing time is 1~5h, solidifies sponge to be placed in the air after finishing to dry naturally, obtains the calcium alginate sponge;
The preparation of d calcium alginate sponge dressing
The calcium alginate sponge that step c obtains is cut, packs, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.
Owing to adopted technique scheme, the useful technique effect of a kind of calcium alginate sponge of the present invention medical dressing and preparation method thereof is:
The sodium alginate that the preparation method of 1 calcium alginate sponge of the present invention adopts two kinds of molecular weight to differ bigger is a raw material, synergism by two kinds of raw materials, regulate the structure of two kinds of proportion of raw materials regulation and control sponges, and with calcium chloride, softening agent and ethanol mixed solution are as coagulating bath, can effectively prevent subsiding of sponge pore space structure, adhesion and sealing, thereby obtained pliability, the all good calcium alginate sponges of elasticity and hygroscopicity, the employing primary freeze drying is shaped, curing and toughness reinforcing technology synchronous and natural air drying prepare pliability calcium alginate sponge, preparation technology is simple and energy consumption is low, reduce production cost, be convenient to promoting the use of of calcium alginate sponge medical dressing.
2 calcium alginate sponges have excellent flexibility, elasticity, breathability, barrier, wearability, water absorption, biocompatibility and degradability and easily remove and hemostatic function, and surfacing is flawless, can be used in various types of skin traumas such as treatment surgical wound, empyrosis wound surface.
The preparation method of calcium alginate sponge of the present invention is simple, technological process is short, energy consumption and production cost are lower, the calcium alginate sponge medical dressing one-shot forming of this method preparation, can replace the calcium alginate non-woven fabric medical dressing, be used for the treatment of various types of skin traumas such as surgical wound, empyrosis wound surface.
The specific embodiment
A kind of calcium alginate sponge medical dressing, calcium alginate sponge medical dressing is by two kinds of sodium alginate blend solutions that molecular weight is different, be shaped through lyophilization, calcium ion crosslinking curing and softening agent are handled and are formed, and wherein the quality percentage composition of each component is respectively in the calcium alginate sponge medical dressing:
Low molecular weight seaweed acid sodium 70%~90%
High molecular sodium alginate 8%~25%
Softening agent 2%~5%
Wherein, the number-average molecular weight of low molecular weight seaweed acid sodium raw materials is 10000~50000, and the number-average molecular weight of high molecular sodium alginate raw material is 300000~500000, and softening agent is a kind of in Polyethylene Glycol or glycerol or 1,3 butylene glycol or the amido silicon oil.
A kind of preparation method of calcium alginate sponge medical dressing, the preparation method of calcium alginate sponge medical dressing comprises the steps:
The preparation of a sodium alginate blend solution
Take by weighing low-molecular-weight sodium alginate according to 4.2%~5.4% of distilled water quality, and it is even to add in the distilled water it to stirring and dissolving, obtain the solution of low molecular weight seaweed acid sodium, take by weighing high-molecular weight sodium alginate according to 0.6%~1.8% of distilled water quality then, add in the above-mentioned solution, stirring at room is even to dissolving, obtains the sodium alginate blend solution.
The sodium alginate that the present invention adopts two kinds of molecular weight to differ bigger is the feedstock production blend solution, low molecular weight seaweed acid south can guarantee that sponge has suitable solid content, thereby pore space structure is more, hygroscopicity and better softness, the high molecular sodium alginate can strengthen the active force between macromole, make compact conformation and elasticity and the good toughness of sponge, non-friable.By the synergism of high molecular sodium alginate and low molecular weight seaweed acid sodium, regulate the ratio between two kinds of raw materials, make that the structure of calcium alginate sponge is appropriate, give elasticity, hygroscopicity and the pliability of sponge excellence.
The preparation of b sodium alginate sponge
The sodium alginate blend solution that step a is made places the cryogenic thermostat device, mechanical agitation limit, limit makes the solution cooling, treat that solution is cooled to 0 ℃~5 ℃ and stops to stir, divide and install in the mould, mould is positioned over pre-freeze in the ultra cold storage freezer, the pre-freeze temperature is-80 ℃~-10 ℃, the pre-freeze time is 1~5h, after pre-freeze is finished mould is placed freezer dryer, baking temperature is-50 ℃~-20 ℃, vacuum is below the 20Pa, and be 6~36h drying time, the sodium alginate sponge that the dry back demoulding obtains being shaped.
In the traditional handicraft, directly put into ultra cold storage freezer after the sodium alginate blend solution prepares and carry out pre-freeze, and the pre-freeze temperature is higher, cause playing drum and producing surface crack of sodium alginate sponge easily, yield rate is lower.The present invention was reduced to 0 ℃~5 ℃ with its temperature earlier before sodium alginate blend solution pre-freeze, reduced the cohesive energy of sodium alginate soln, the energy that has reduced in the pre-freeze process discharges, quickened the moving process of pre-freeze, can avoid playing drum and producing surface crack in the sodium alginate sponge pre-freeze process, make sponge surfacing, exquisiteness, and yield rate is higher.In addition, mechanical agitation is followed the solution temperature-fall period, and the sponge structure heterogeneity that can avoid local cooling to cause easily produces defectives such as crack.
The preparation of c calcium alginate sponge
Take by weighing softening agent according to 2%~5% of ethanol quality, the softening agent that takes by weighing is added in the ethanol, be stirred to mix homogeneously, obtain the mixed solution of ethanol and softening agent, take by weighing calcium chloride according to 3%~6% of ethanol quality then, add the calcium chloride that takes by weighing in above-mentioned mixed solution stirring and dissolving, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge that step b is obtained is immersed in and carries out crosslinking curing in the above-mentioned coagulating bath, the crosslinking curing temperature is 25 ℃~40 ℃, the crosslinking curing time is 1~5h, solidifies sponge to be placed in the air after finishing to dry naturally, obtains the calcium alginate sponge.
The coagulating bath of sodium alginate sponge is a calcium chloride water in the traditional handicraft, because the sodium alginate sponge is water-soluble, in the process of setting part pore space structure of sodium alginate sponge cave in, adhesion and sealing, make and the compact structure of calcium alginate sponge, hard, embrittlement and lack flexibility to be used for tissue engineering bracket.The present invention is with the coagulating bath as the sodium alginate sponge of calcium chloride, softening agent and ethanol mixed solution, because the sodium alginate sponge is insoluble to ethanol, the problem that can avoid traditional calcium alginate sponge to exist obtains all good calcium alginate sponges of pliability and elasticity.In addition,, do not need to handle, air-dryly under the natural conditions just can obtain exsiccant calcium alginate sponge, saved the energy, reduced cost through secondary forming and hyperthermia drying because ethanol is easy to volatilization.
The soft toughness reinforcing way of traditional sponge is that softening agent is added in the solution before the pre-freeze, owing between softening agent and the aqueous solution stronger active force is arranged, prolonged freeze-off time and the drying time of sponge, and control does not easily cause the adhesion and the sealing of sponge pore space structure at that time.The present invention adopts the sponge toughness reinforcing technology in back that is shaped, and can reduce pre-freeze and drying time, energy savings, and realize the toughness reinforcing of sponge simultaneously solidified, shortened technological process.
The preparation of d calcium alginate sponge dressing
The calcium alginate sponge that step c obtains is cut, packs, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.
Describe in further detail below in conjunction with the preparation method of specific embodiment the non-ironing cellulose fibre of high resiliency of the present invention:
Embodiment 1
Take by weighing 100 gram distilled water, 4.2 gram-molecular weights successively and be 50000 sodium alginate, 1.8 gram-molecular weights and be 300000 sodium alginate, add to two kinds of sodium alginate raw materials that take by weighing in the distilled water successively while stirring, stirring at room obtains the sodium alginate blend solution to dissolving; Blend solution is placed the cryogenic thermostat device, in the limit cooling of the following mechanical agitation of 0 ℃ of condition, treat that solution is cooled to 0 ℃ and stops to stir, divide to install in the mould, mould is placed ultra cold storage freezer pre-freeze, in-80 ℃ of pre-freeze 1h, then mould is placed freezer dryer, vacuum in the control dry run is below the 20Pa, handles 6h, the sodium alginate sponge that the dry back demoulding obtains being shaped in-50 ℃; Take by weighing ethanol, 2 gram Polyethylene Glycol, the 3 gram calcium chloride of 100 grams successively, add to Polyethylene Glycol in the ethanol and stir, obtain the mixed solution of ethanol and Polyethylene Glycol, then the calcium chloride that takes by weighing is added in the above-mentioned mixed solution, be stirred to the calcium chloride dissolving evenly, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge is immersed in the above-mentioned coagulating bath, in 25 ℃ of crosslinking curing 5h, solidify sponge to be placed in the air after finishing and dry naturally, obtain the calcium alginate sponge; With the cutting of calcium alginate sponge, packing, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.
Embodiment 2
Take by weighing 100 gram distilled water, 5.4 gram-molecular weights successively and be 10000 sodium alginate, 0.6 gram-molecular weight and be 500000 sodium alginate, add to two kinds of sodium alginate raw materials that take by weighing in the distilled water successively while stirring, stirring at room obtains the sodium alginate blend solution to dissolving; Blend solution is placed the cryogenic thermostat device, in the limit cooling of the following mechanical agitation of 0 ℃ of condition, treat that solution is cooled to 1 ℃ and stops to stir, divide to install in the mould, mould is placed ultra cold storage freezer pre-freeze, in-10 ℃ of pre-freeze 5h, then mould is placed freezer dryer, vacuum in the control dry run is below the 20Pa, handles 36h, the sodium alginate sponge that the dry back demoulding obtains being shaped in-20 ℃; Take by weighing ethanol, 3 gram glycerol, the 4 gram calcium chloride of 100 grams successively, add to glycerol in the ethanol and stir, obtain the mixed solution of ethanol and glycerol, in the above-mentioned mixed solution, be stirred to the calcium chloride dissolving evenly in then the calcium chloride that takes by weighing being added to, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge is immersed in the above-mentioned coagulating bath, in 30 ℃ of crosslinking curing 4h, solidify sponge to be placed in the air after finishing and dry naturally, obtain the calcium alginate sponge; With the cutting of calcium alginate sponge, packing, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.
Embodiment 3
Take by weighing 100 gram distilled water, 4.5 gram-molecular weights successively and be 20000 sodium alginate, 1.5 gram-molecular weights and be 350000 sodium alginate, add to two kinds of sodium alginate raw materials that take by weighing in the distilled water successively while stirring, stirring at room obtains the sodium alginate blend solution to dissolving; Blend solution is placed the cryogenic thermostat device, in the limit cooling of the following mechanical agitation of 0 ℃ of condition, treat that solution is cooled to 2 ℃ and stops to stir, divide to install in the mould, mould is placed ultra cold storage freezer pre-freeze, in-20 ℃ of pre-freeze 4h, then mould is placed freezer dryer, vacuum in the control dry run is below the 20Pa, handles 30h, the sodium alginate sponge that the dry back demoulding obtains being shaped in-30 ℃; Take by weighing ethanol, 4 grams 1 of 100 grams successively, 3-butanediol, 5 gram calcium chloride, with 1, the 3-butanediol adds in the ethanol and stirs, obtain ethanol and 1, the mixed solution of 3-butanediol, then the calcium chloride that takes by weighing is added in the above-mentioned mixed solution, be stirred to the calcium chloride dissolving evenly, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge is immersed in the above-mentioned coagulating bath, in 35 ℃ of crosslinking curing 3h, solidify sponge to be placed in the air after finishing and dry naturally, obtain the calcium alginate sponge; With the cutting of calcium alginate sponge, packing, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.
Embodiment 4
Take by weighing 100 gram distilled water, 5 gram-molecular weights successively and be 40000 sodium alginate, 1 gram-molecular weight and be 450000 sodium alginate, add to two kinds of sodium alginate raw materials that take by weighing in the distilled water successively while stirring, stirring at room obtains the sodium alginate blend solution to dissolving; Blend solution is placed the cryogenic thermostat device, in the limit cooling of the following mechanical agitation of 0 ℃ of condition, treat that solution is cooled to 5 ℃ and stops to stir, divide to install in the mould, mould is placed ultra cold storage freezer pre-freeze, in-60 ℃ of pre-freeze 4h, then mould is placed freezer dryer, vacuum in the control dry run is below the 20Pa, handles 10h, the sodium alginate sponge that the dry back demoulding obtains being shaped in-40 ℃; Take by weighing ethanol, 5 gram amido silicon oils, the 6 gram calcium chloride of 100 grams successively, add to amido silicon oil in the ethanol and stir, obtain the mixed solution of ethanol and amido silicon oil, then the calcium chloride that takes by weighing is added in the above-mentioned mixed solution, be stirred to the calcium chloride dissolving evenly, obtain the coagulating bath of sodium alginate sponge, the sodium alginate sponge is immersed in the above-mentioned coagulating bath, in 40 ℃ of crosslinking curing 1h, solidify sponge to be placed in the air after finishing and dry naturally, obtain the calcium alginate sponge; With the cutting of calcium alginate sponge, packing, then through Co
60Irradiation sterilization obtains calcium alginate sponge medical dressing.