CN104784741B - chitosan functional hydrocolloid medical dressing - Google Patents
chitosan functional hydrocolloid medical dressing Download PDFInfo
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- CN104784741B CN104784741B CN201510196392.8A CN201510196392A CN104784741B CN 104784741 B CN104784741 B CN 104784741B CN 201510196392 A CN201510196392 A CN 201510196392A CN 104784741 B CN104784741 B CN 104784741B
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Abstract
The present invention relates to a kind of chitosan functional hydrocolloid medical dressing, its main component is:Polymer elastomer 10% 40%, tackifying resin 5% 20%, neutral hydrocolloid 5% 15%, polyanion hydrocolloid 15% 40%, polycationic hydrocolloid 3 15%, various additives 5% 25%, the percentage is weight percentage.Chitosan functional hydrocolloid medical dressing provided by the invention has the performances such as fabulous gas permeability, absorbability, flexibility, viscosity and the good stickiness of skin, wherein the chitosan added serves anti-inflammation, hemostasis, the effect for promoting wound healing in dressing.The dressing is especially suitable for various scratches, burn, bedsore and various wounds.
Description
Technical field
The present invention relates to a kind of hydrocolloid medical dressing, particularly a kind of chitosan functional hydrocolloid medical dressing.
Background technology
Hydrocolloid medical dressing is manufactured a kind of high-tech after particle and rubber mix water-soluble high-molecular substance
Cure the wound and use material, be a kind of very important wound dressing used in current clinical care.
Rubber constituent in hydrocolloid medical dressing has certain viscosity so that this kind of dressing, which very easily applies, is hindering
On mouth, hydrocolloid fully expands after absorbing moisture, and its bonding force has declined so that the bonding of bearing hydrocolloid dressing and wound is main
Occur on the healthy skin of wound perimeter;On the other hand, this kind of dressing has highly hydrophilic, can be tieed up on the surface of wound
The healing environment of a moistening, and absorbing wound exudate are held, can best protect the fresh granulation tissue on the surface of a wound.Cause
And the main function of hydrocolloid medical dressing is to provide stickup property and keeps the healing environment of wound moist, but for promoting
Wound healing and hemostasia effect and unobvious.
Chitosan, also known as chitosan, are a kind of macromolecule glycosaminoglycans obtained after chitin deacetylation, Ye Shitian
Unique alkaline polysaccharide in right polysaccharide.Chitosan has good biocompatibility, biology as a kind of natural macromolecular material
Degradability, bioactivity, and with the effect such as antibacterial, anti-inflammatory, hemostasis, immune, while the shell of different molecular weight ranges gathers
Sugar has different property to the activity of blood, and as low-molecular weight chitoglycan has an anticoagulant property, high molecular weight chitosan has rush solidifying
Courage and uprightness, this healing of a series of performance for the surface of a wound play vital effect.At present, chitin, chitosan are made
Medical dressing proved by numerous scholar's research relative to effect of traditional cotton gauze to wound healing.
At present, the hydrocolloid medical dressing promotion wound-healing abilities of in the market are poor, haemostatic effect is undesirable, shape is kept
Property difference the problems such as, and chitosan medical dressing and skin attachement are poor, absorb sepage after the problems such as being easy to come off, it is above-mentioned for solution
Problem, the invention provides a kind of chitosan feature water for the defects of overcoming chitosan medical dressing and hydrocolloid medical dressing
Colloid medical dressing.
The content of the invention
The invention aims to provide a kind of chitosan functional hydrocolloid medical dressing, the dressing has fabulous
The performances such as gas permeability, absorbability, flexibility, viscosity and the good stickiness of skin, wherein the chitosan added rises in dressing
Anti-inflammation, hemostasis, the effect for promoting wound healing have been arrived, has overcome chitosan medical dressing and hydrocolloid medical dressing each
The defects of.
Chitosan feature bearing hydrocolloid dressing of the present invention can be prepared into difference according to the demand of corporal parts
Thickness, shape, size, and needed according to patient wound to select different base materials(Such as:PU ventilated membranes, spunlace non-woven cloth, punching
Ventilated membrane etc.), suitable for the nursing and dressing of the wound surface of a wound such as various scratches, burn, bedsore, various wounds.
Herein, term " water soluble polymer " is a kind of high polymer material of strongly hydrophilic, can be dissolve or swell in
The aqueous solution or dispersion are formed in water.Contain substantial amounts of hydrophilic radical in the molecular structure of water-soluble polymer.Hydrophilic group
Group can be generally divided into three classes:Cation group:Tertiary amine groups, quaternary amine base etc.;Anionic group:Carboxylic acid group, sulfonic group, phosphoric acid
Base, sulfate etc.;Polar nonionic group:Hydroxyl, ether, amido, amide groups etc..
Herein, term " hydrophilic colloid " refers to be dissolved in water, and under certain conditions abundant aquation formed it is glutinous
Thick, satiny solution or the polymer substance of colloid.
Herein, term " hydrocolloid " refers to water-soluble high-molecular material, and this kind of material absorbs energy after moisture in water
A kind of colloidal material is swelled into, is a kind of very strong material of hydrophily.
The solution that the present invention is taken:A kind of chitosan functional hydrocolloid medical dressing, polymer elasticity are provided
Body 10%-40%, tackifying resin 5%-20%, neutral hydrocolloid 5%-15%, polyanion hydrocolloid 15%-40%, polycation glue
Body 3-15%, various additives 5%-25%, the percentage are weight percentage.
Described polyanion hydrocolloid is in pectin, sodium carboxymethylcellulose, alginate, antler glue, xanthans
One or more mixtures, preferably carboxymethyl cellulose sodium;Described polycationic hydrocolloid is chitosan hydrochloride, shell
One or more mixtures in glycan lactate, glutamate and other chitosan derivatives;Described neutrality
Hydrocolloid is one or more mixtures in guar gum, gelatin, locust bean gum angle, preferably guar gum;Described increasing
Viscosity resin is rosin, one kind in rosin derivative, terpenoid resin, Petropols, preferably rosin and its derivative, more preferably
Rosin resin.
Described chitosan is a kind of glycosaminoglycan of the extraction gained from crustacean, through new made from acylation reaction
Chitosan derivatives.The chitosan derivative is aminobenzoyl chitosan derivatives, and its preparation method is:P-aminophenyl
Formic acid and thionyl chloride reaction generation p-benzoyl chlorine, under supersonic oscillations, p-benzoyl chlorine and chitosan
Acetic acid solution is mixed with to obtain para aminobenzoyl chitosan derivative, and acetone carries out surname extraction, must produced after vacuum drying
Thing.
The weight percent concentration of the acetic acid solution of the chitosan is 1%, the p-benzoyl chlorine and chitosan
Dosage weight ratio is 3:1.
Aminobenzoyl chitosan derivatives have following characteristic:Deacetylation 80.0%-90.0%, pH 4-6, dry and lose
Weight≤15.0%, ash≤1.0%, viscosity≤200mpa.s, total number of bacteria≤1000cfu/g, fungi count≤100cfu/g.
Polyisobutene, the molecule that polymer elastomer used includes styrene series elastomer, molecular weight is 1000-5000
Measure the polyisobutene for 80000-120000, liquid rubber etc..As mentioned styrene series elastomer in polymer elastomer, point
The polyisobutene and the dosage weight of liquid rubber that polyisobutene, the molecular weight that son amount is 1000-5000 are 80000-120000
Than for 4:2:1:1.
Liquid rubber used is polyisoprene liquid rubber, and molecular weight 30000-60000, Tg are -63 DEG C, are being applied
Play a part of plasticising in material, viscosity and flexibility are provided.
Styrene series elastomer used is SIS(SIS), hydrogenation of benzene second
Alkene-butadiene rubber(HSBR), styrene-ethylene/propylene-styrene block copolymer(SEPS), styrene-butadiene-benzene
Ethylene block copolymer(SBS), styrene-ethylene/butylene-alkene crystalline block copolymers(SEBC), styrene-ethylene/second
Alkene/propylene-styrene block copolymer(SEEPS)(It is commercially available prod)In one or more mixtures.It is preferred that SIS.
Polyisobutene used is compounded from the polyisobutene of different molecular weight, wherein, molecular weight is accounting for for 1000-5000
The 50%-80% of polyisobutene total amount;Molecular weight is the 80000-120000 20%-50% for accounting for polyisobutene total amount.
Various additives used are plasticizer, antiseptic, preservative, antioxidant, pH adjusting agent etc..
Plasticizer used is one kind in the synthesis plasticizer, petroleum series plasticizer, liquid rubber of dibasic acid ester.
Role is as follows in the product for primary raw material described in technical solution of the present invention:1. styrene series elastomer
Play a part of a kind of rubber substrate, during mixing, hydrophilic macromolecule is dispersed on the rubber substrate;2. gather
Isobutene rubber has the performances such as water resistance and low-temperature pliability, and middle low molecule amount polyisobutene has cold flow and viscosity, can made
For softening agent and tackifier, because polyisobutene is without double bond, cohesive strength is very low, easily cracking, and when temperature raises, middle low molecule
The aggravation of polyisobutene cold flow is measured, therefore uses the tearing toughness and cold flow of low molecule amount in high molecular weight polyisobutylene improvement;③
Chitosan has hemostasis, promotes wound healing, the effect such as antibacterial, at the same as polycationic hydrocolloid chitosan with other water-soluble
Property high polymer material compounding, the water imbibition and integrality of product can be improved;4. pectin and guar gum play thickening, absorb sepage
Effect.
The preparation method of chitosan functional hydrocolloid medical dressing product of the present invention is as follows:Weighed according to formula
Good various raw materials, the raw materials such as rubber-like, tackifying resin, plasticizer are added in banbury, are 135 DEG C -160 DEG C in temperature
Under, pumping vacuum and mixing 20-30min, when temperature drops to 80 DEG C -100 DEG C, by neutral colloid, polyanion colloid, poly- sun from
Sub- colloid is added, and is discharged after pumping vacuum and mixing 30-45min, and in the case where temperature is 70 DEG C -90 DEG C, various thickness are molded into vulcanizer
The sheet material of degree, simultaneously can have PU ventilated membranes, spunlace non-woven cloth etc., according to demand, mould with release liners or mould release membrance, another side
It is cut into variously-shaped.
Embodiment
With reference to specific implementation case to the composition of chitosan feature bearing hydrocolloid dressing of the present invention, preparation,
Performance is further described, with help those skilled in the art to the present invention inventive concept, technical scheme have more comprehensively,
It is more accurate, deeper into understanding.
Embodiment
The material context used in embodiment is as described below:
P-aminobenzoic acid:Nanjing chemical reagent limited company
Thionyl chloride:Jinan Ying Dong Science and Technology Development Co., Ltd.s
SIS(SIS):KratonD-1161NS rises in section of the U.S.
Polyisobutene(PIB1):South Korea great Lin PB2400, molecular weight 2400
Polyisobutene(PIB2):BASF B15FSN, molecular weight 80000
Liquid rubber:Kuraray LIR-50, molecular weight 54000, Tg are -63 DEG C
Guar gum:Zhengzhou three and bio tech ltd
Sodium carboxymethylcellulose(CMC):Zhengzhou prosperity food additives Co., Ltd
Ac-Di-Sol(X-CMC):JRS PHARMA, pH 5-7
Chitosan:Jinan Haidebei Marine Organism Engineering Co., Ltd.
Aminobenzoyl chitosan derivatives:Self-control
Rosin resin:Guangdong Zhong Ye rosin Co., Ltd
Naphthenic oil:Shanghai Xinhua lubricating oil plant, No. 4010
Antioxidant:Nanjing chemical plant, 1010
Embodiment 1:P-aminobenzoic acid is put into three-necked bottle, absolute ether is added, dissolving, adds somewhat excessive
Thionyl chloride, be put into ultrasonic cleaner, supersonic oscillations 10min, continue back flow reaction and be cooled to room temperature, reaction is completed
After be evaporated under reduced pressure, untill no liquid steams, after recrystallization, obtain p-benzoyl chlorine.Added into three-necked bottle a certain amount of
Concentration be 1% chitosan acetic acid solution, then add p-benzoyl chlorine(Chitosan acetic acid solution and p-aminophenyl first
The usage ratio of acyl chlorides is 3:1), react, stand overnight under supersonic oscillations.After the completion of reaction, adding a large amount of acetone makes production
Thing is precipitated out, and is filtered, then with after the mixed solvent of absolute ethyl alcohol and absolute ether immersion 24h, is filtered, filter cake is carried out with acetone
Surname extraction 24h, aminobenzoyl chitosan derivatives are obtained after vacuum drying.
Embodiment 2:It is formulated as 16 parts by weight SIS, 8 parts by weight PIB1,4 parts by weight PIB2,4 parts by weight LIR-50,10 weights
Measure part guar gum, 14 parts by weight CMC, 10 parts by weight X-CMC, 5 parts by weight chitosans, 15 parts by weight rosin resins, 13 weight
Part naphthenic oil, 1 parts by weight 1010.
Embodiment 3:It is formulated as 18 parts by weight SIS, 8 parts by weight PIB1,4 parts by weight PIB2,4 parts by weight LIR-50,10
Parts by weight guar gum, 14 parts by weight CMC, 10 parts by weight X-CMC, 5 parts by weight aminobenzoyl chitosan derivatives, 15 weights
Measure part rosin resin, 13 parts by weight naphthenic oils, 1 parts by weight 1010.
Various raw materials are weighed according to the formula described in embodiment 2, embodiment 3, by rubber-like, tackifying resin, additive
Deng raw material, it is added in banbury, in the case where temperature is 135 DEG C -160 DEG C, pumping vacuum and mixing 20-30min, treats that temperature drops to 80
At DEG C -100 DEG C, neutral colloid, polyanion colloid, polycationic colloid are added, discharged after pumping vacuum and mixing 30-45min,
In the case where temperature is 70 DEG C -90 DEG C, the sheet material that thickness is 1mm is molded into vulcanizer, it is another simultaneously with release liners or mould release membrance
Face can have PU ventilated membranes, according to testing requirement, be die-cut to corresponding shape.
Embodiment 4,5,6 be chitosan and aminobenzoyl chitosan derivatives to staphylococcus aureus, aspergillus niger,
The contrast situation of the bacteriostasis rate of Escherichia coli(It is shown in Table 1).
Table 1
As known from Table 1, chitosan and para aminobenzoyl chitosan derivative are to staphylococcus aureus, aspergillus niger, big
The fungistatic effect of enterobacteria increases and strengthened with concentration, but the fungistatic effect of para aminobenzoyl chitosan derivative is substantially excellent
In chitosan.
Chitosan bearing hydrocolloid dressing sample prepared by embodiment 2,3 is attached to the small white mouse of wound by embodiment 7,8,
After patch examination 3 days, it is found that the dressing added with para aminobenzoyl chitosan derivative becomes apparent to wound-healing abilities.Shell gathers
Sugar has hemostasis, promotes the effect such as wound healing, antibacterial, and the fungistatic effect of para aminobenzoyl chitosan derivative is more preferable.Together
The Chitosan-phospholipid complex of Shi Zuowei polycationic hydrocolloids compounds with other water-soluble high-molecular materials, can improve product
Water imbibition and integrality, a wet environment is created for wound, in gentle environment, the various types of cells in wound is swashed
It is living, the pathogenic microorganisms in wound is swallowed, accelerates the healing of wound.
Note:
The measure of bacteriostasis rate
In terms of microbiology angle, the growth of bacterium is increasing as mark using number of groups, and mould is then with bacterium
The quality of silk or increasing to weigh growing state for volume.For bacterium using colony counting method measure chitosan and derivative
Bacteriostasis rate.
Prepare the chitosan of different quality containing easily and derivative is easy(0.5% acetum is solvent), respectively will
The sample solution of 0.1mL bacteriums bacteria suspension and 0.1mL various concentrations is uniformly coated on culture medium flat plate, and blank is only plus bacterium is hanged
Liquid is without adding sample solution.All flat boards cultivate 24h in 37 DEG C of constant incubators, take out the bacterial growth for observing each flat board
Situation, calculate bacteriostasis rate.
The calculating of bacteriostasis rate:η=(N1-N2)/N1×100%
Wherein N1, N2Respectively blank plate and the clump count on the flat board for scribbling sample.
For aspergillus niger using dry weight method measure chitosan and the bacteriostasis rate of derivative, the shell for configuring different quality containing gathers
Sugar juice and derivative solution(0.5% acetum is solvent).Respectively by 1mL black-koji moulds suspension and 2mL various concentrations
Sample solution is added in fluid Sabouraud culture medium, and blank is only adds equal bacteria suspension without adding sample solution, in 28 DEG C of constant temperature shakes
Swing and 48h is cultivated in incubator, filter, dry and dry cell weight of weighing, calculate bacteriostasis rate.
The calculating of bacteriostasis rate:η=(W1-W2)/W1×100%
Wherein W1, W2Respectively it is not added with mycelia weight in the mycelia weight and addition sample culturing liquid in sample culturing liquid.
Claims (8)
1. a kind of chitosan functional hydrocolloid medical dressing, it is characterised in that be made by the raw material of following percentage by weight:It is poly-
Compound elastomer 10%-40%, tackifying resin 5%-20%, neutral hydrocolloid 5%-15%, polyanion hydrocolloid 15%-40%, poly- sun
Hydrocolloid 3%-15%, additive 5%-25%;Described polycationic hydrocolloid is that chitosan prepares gained through acylation reaction
A kind of chitosan derivatives;Described polymer elastomer includes styrene series elastomer, molecular weight is the poly- of 1000-5000
Isobutene, the polyisobutene and liquid rubber that molecular weight is 80000-120000, styrene series elastomer, molecular weight 1000-
The polyisobutene and liquid rubber dosage weight ratio that 5000 polyisobutene, molecular weight are 80000-120000 are 4:2:1:1.
2. chitosan functional hydrocolloid medical dressing according to claim 1, it is characterised in that described polyanion
Hydrocolloid is one or more mixtures in pectin, sodium carboxymethylcellulose, alginate, antler glue, xanthans;Institute
The neutral hydrocolloid stated is one or more mixtures in guar gum, gelatin, locust bean gum angle;Described tackifying resin
For one kind in rosin, rosin derivative, terpenoid resin, Petropols.
3. chitosan functional hydrocolloid medical dressing according to claim 1, it is characterised in that the chitosan derivative
Thing is aminobenzoyl chitosan derivatives, is made by laxative remedy:P-aminobenzoic acid and thionyl chloride reaction generation p-aminophenyl
Formyl chloride, under supersonic oscillations, the acetic acid solution of p-benzoyl chlorine and chitosan is mixed with to obtain p-aminophenyl first
Acyl chitosan derivatives, acetone carry out surname extraction, obtained after vacuum drying.
4. chitosan functional hydrocolloid medical dressing according to claim 3, it is characterised in that the second of the chitosan
The weight percent concentration of acid solution is 1%, and the dosage weight ratio of the p-benzoyl chlorine and chitosan is 3:1.
5. chitosan functional hydrocolloid medical dressing according to claim 3, it is characterised in that described aminobenzoic
Acyl chitosan derivatives substitution value≤0.79, solubility≤0.0258g/mL, pH 4-6, loss on drying≤15.0%, ash≤
1.0%th, viscosity≤200mpa.s, total number of bacteria≤1000cfu/g, fungi count≤100cfu/g.
6. chitosan functional hydrocolloid medical dressing according to claim 1, it is characterised in that described liquid rubber
For isoprene liquid rubber, molecular weight 30000-60000, Tg are -63 DEG C.
7. chitosan functional hydrocolloid medical dressing according to claim 1, it is characterised in that described polystyrene
Elastomer is SIS, hydrogenated styrene-butadiene rubber, styrene-ethylene/the third
Alkene-styrene block copolymer, SBS, styrene-ethylene/butylene-alkene crystallization
One or more mixtures in block copolymer, styrene-ethylene/ethylene/propene-styrene block copolymer.
8. chitosan functional hydrocolloid medical dressing according to claim 1, it is characterised in that polyisobutene used
Compounded from the polyisobutene of different molecular weight, wherein, molecular weight is the 1000-5000 50%- for accounting for polyisobutene gross weight
80%;Molecular weight is the 80000-120000 20%-50% for accounting for polyisobutene gross weight.
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