CN1054539A - The composite gauze material of non-linting - Google Patents

Abstract

Durable, not lint hair, water absorption, the composite that can dangle in fact that are used for wound dressing, be with hydrophilic polymer coated fiber cellulose fiber, the latter can be out rare woven cotton gauze, this polymer can be the polyurethane foam prepolymer, as the end capped Polyethylene Glycol of toluene-2,4-diisocyanate, preferably contain surfactant.The also available poly(ethylene oxide) of this polymer, carboxymethyl cellulose, polyvinylpyrrolidone.When using polyurethane, water is about 6: 1 to 400: 1 to polymer ratio

Description

The composite gauze material of non-linting

The present invention relates in fact the not cotton cloth of lint hair.More specifically say to relate to durable, hydrophilic, not lint hair, water absorption, the composite that can dangle in fact, it comprises the hydrophilic polymer resin that is applied on the cellulosic fibre material.

Cotton cloth is to be made by the cotton fiber of twisting, and through cleaning, bleach and sterilization.In cleaning and bleaching process, cotton thread is subjected to chemical treatment, and is combined with residual starch, protein, casein and resin.These materials can come off and contaminated wound from cotton cloth together with fiber fines.In surgical operation, they can enter in the body and not discovered, and cause granuloma, but perhaps intravasation system and cause more serious symptoms.

In recent years, take off the velveteen problem and caused FDA(U.S. food and medicine administrative bureau) attention.FDA is taking measures to set up performance standard for the gauze that relates to the lint problem.Its about to suggestion be in the commentary of regulations of 51 kinds of common and plastics surgical instruments classification, such narration is arranged: " FDA agrees that present document points out with gauze contact particulate matter problem, still not have " safety " standard for interior ".53（122）Fed.Reg.23，867（1988）。Also narrate: " FDA believes, needs a cover performance standard to come the design and the manufacturing of control [gauze], pollutes to alleviate particulate matter, and guarantees sufficient radiopacity ".53（122）Fed，Reg.23，866（1988）。Therefore, for the wrapper material that is used for wound, need a kind of material of non-linting in fact.

Behind any surgical operation, it is serious problems that attachment is arranged in wound.There is an author to point out, " at present; intra-abdominal adhesions is ileac common cause; the great majority of adhesion are that the people is for causing " Ellis, " Internal Overhealing:The Problem of Intraperitoneal Adhesions ", World J.of Surg., 4(3) 303-306(1980).For a long time generally acknowledge that surgical cloth may be this adhesion and granulomatous source.Promptly there was the author to point out as far back as 1966, " evidence suggests that the fragment of being brought into by gauze can cause granuloma and deposit fiber shape tissue when operation ".Sturdy etc., " Surgical Sponges:A Cause of Granuloma and Adhesion Formation ", Ann.of Surg.165(1) 128-134(1967).

Though the cellulose gauze is hydrophilic, cellulose fibre generally can't be decomposed by human enzyme system.This cellulose fibre of long-term existence makes the patient that immunoreation take place after operation, causes inflammation and adhesion.Use woven cotton swab, too much use the non-woven cotton swab, this problem is even more serious significantly.See Levinson ﹠amp; Swolin, " Postoperative Adhesions:Etiology, Prevention, and Therapy ", Clin.Obst.﹠amp; Gyn., 23(4); 1213-1220(1980).

Come the replace cotton gauze so studied composite.These materials are not that hydrophilic is lower than gauze, ruggedness is lower than gauze, are exactly that drapability is lower than gauze.The absorbability of gauze and hydrophilic are very important, because its main function is as absorbing material in surgical operation and wound healing process.If this composite is not durable, will stay the fine hair deposit, and also can be like this after operation.The also necessary tool drapability of this composite, or conformal performance are so that adapt to the bodily form, for example abdominal part in the surgical operation.Therefore, need provide durable, not lint hair, tool drapability absorbent composite, be used as the wound dressing material.

The present invention relates to the wound dressing material, this material is lint hair and tool high-hydroscopicity very not in fact.Composite of the present invention comprises a kind of thin woven cellulosic fibre material, as cotton cloth, and with a kind of hydrophilic polymer external coating.Though use polymer-coated mistake, this composite be still high-absorbable, tool drapability, elasticity and nontoxic, therefore be suitable for succedaneum as surgical operation gauze commonly used.

Wound dressing material of the present invention comprises the thin woven cellulose fibre with warp thread and weft yarn.These yarns are coated with a kind of hydrophilic polymer film, and the part that each line is knitted between the mark is opened rare.Believe that this polymer hydroxyl special and on the cellulose combines and eliminated free particulate matter in fact.This cellulosic fibre material can be woven cotton cloth, can be used for surgical operation and wound dressing.This polymer can be a kind of polyurethane foam prepolymer, is applied on the gauze with aqueous solution state.Another way, this polymer can be a kind of poly(ethylene oxide) or carboxymethyl cellulose, or polyvinylpyrrolidone.Preferred polymer is the end capped Polyethylene Glycol of toluene-2,4-diisocyanate, i.e. the TREPOL of Twin Rivers Engineering supply ^TM, Boothbay, Maine.This prepolymer aqueous solution can contain a kind of surfactant, as Pluronic The F68(BASF supply), to guarantee moistening.The polymer that is used to be coated with this cellulose fibre can be a blend, and its water is about 6: 1 to 400: 1 to the ratio of prepolymer.This blend can increase the water absorbability energy, compares with untreated cotton cloth to surpass 100%, usually surpasses 200%.The water absorbability of polymer-coated cellulose fibre of the present invention is compared with the untreated fibers cellulose fiber, and the former is 3-4.5 a times of dry gauze weight for about 300-450%(absorbs water weight), the about 200-250% of the latter.

Importance of the present invention is that water should have enough usefulness that particulate matter and resin chip are clung to polymer ratio in the coating composition, but do not reduce hydrophilic, drapability or elasticity, keep original rare weaving structure of opening simultaneously.Therefore, the engineer in present technique field can make polymer-coated cellulosic fibre material as the wound dressing material according to this paper disclosure content.

The object of the invention provides the cotton cloth of a kind of non-linting in fact, water absorption, durable, tool drapability.

By explanation hereinafter, accompanying drawing, claim is illustrated the other objects and features of the invention.

Fig. 1 illustrates undressed woven cellulosic fibre material, shows warp and parallel here;

Fig. 2 is a schematic detail view, represents untreated warp and the infall of the parallel that is untreated, and shows not agglutinating particulate matter and resin-like fragment;

Fig. 3 is a schematic detail view, the part cutaway view after expression is coated with yarn by the present invention;

Fig. 4 also is warp and parallel infall, but by the polymer-coated mistake of the present invention;

Fig. 5 is the equipment sketch map by the inventive method coating cellulose fibrous material.

Fig. 1 draws typical woven cotton gauze 10, and warp 12 and parallel 14 are wherein arranged, and defines zone 16 between warp and parallel stitching after being made into.Owing to there is zone between this stitching, make this material be out rare weaving goods, help its water absorption.

Each bar line of cotton cloth 10 all is the twisting thing of many cotton fibers 11.The main component of cotton fiber 11 is celluloses.Be indicated in Merrill, Macormac ﹠amp; Mauersberger, Ameri-can Cotton Handbook, 88-89(1949).Making the natural cotton fiber obvolvent is hydrogen bond force between the cellulosic hydroxyl to together strength.The structure of cotton fiber 11 is many dehydrated glucose units and is connected by the oxo bridge between 1: 4 carbon atom, becomes long cellulose chain.Except that containing anhydroglucose, also contain other materials such as protein, wax, pectin in the cotton fiber 11.Therefore, natural cotton fiber attaches some particulate matter.The cotton gauze 10 that is mainly used in wound dressing is to be made by the cotton fiber of twisting, and through cleaning, bleach and sterilization.In cleaning and bleaching process, yarn touches the chemical treatment medicament, comprises acid, enzyme, alkali, soda, sodium silicate, chlorine, sodium hydroxide, sulphuric acid, soda silicate, turkey red oil, hydrogen peroxide.

The processing cotton fiber causes residual starch, protein, casein, resin down.These materials can in use come off from cotton cloth together with the fiber fines head.Can not stay in the wound when binding up a wound with cotton cloth in conjunction with graininess cotton fiber material 20 and resin-like chip 22 shown in Fig. 2 causes adhesion and granuloma.

As shown in Figure 3, can cover each bar warp and parallel with polymer coating 25.Fig. 3 and 4 illustrate any by the present invention by polymer coating 25 bonded particulate shape cotton fiber material 20 and resin-like chips 22.Please note that the space 16 between the stitching among Fig. 4 keeps opening, and is not aggregated 25 fillings of thing coating.This is very important for keeping high water absorption.

As shown in Figure 4, polymer coating becomes polymer " fillet " 18 in the corner of the infall of the warp 12 of this composite gauze material and parallel 14.This fillet 18 is to be positioned at warp and the parallel place that meets, and is to connect institute by polymer to constitute.They make this material in use keep opening rare weaving structure better.If untreated cotton cloth, the resistance of pair linear deformation is just arranged, but this gauze has the tensile strength that fillet 18 can be promoted material laterally just being torn easily.

The manufacturing of composite is that one deck hydrophilic polymer membrane is applied on the preform weaving fiber cellulose fiber material (as common gauze) of type shown in Figure 1.Several unconjugated hydroxyls are arranged on the cellulose, and they can form covalent bond with the hydrophilic polymer reaction.Cellulose can combine with the polymer that adds as the hydroxyl donor.The polymeric system that is used to form coating generally is a kind of thermoset prepolymer mixture, and is dissolved in the water quality carrier; Become after this crosslinked polymer and be water-insoluble.For obtaining the coating of coating cotton thread, and make gauze keep opening rare weaving structure, the viscosity of this solution is very important.Under concrete condition, the viscosity of coating solution and wettability control are the ratios by regulating prepolymer/water and mix various surfactants.

Press one aspect of the present invention, what chemical treatment was used is the poly(ethylene oxide) that Uniom Carbide provides.This polymer can with such as chemical compound good combination such as carboxymethyl celluloses, and with hydroxyl donor such as the cellulose activity that responds.This poly(ethylene oxide) can be mixed with the ratio of carboxymethyl cellulose with 1: 1.In the one embodiment, poly(propylene oxide) and methylcellulose are mixed into 6%(weight with water respectively) solution, and then admixed together with 1: 1.Become solution to be applied over this gauze institute.This solution and gauze are crosslinked under radiation parameter, and form insoluble hydrophilic film in solidification process, wrap on the every one thread that has free particles.This complex can absorb the water of 1400 times of its weight nearly or more.In another program of the present invention, used chemical treatments is polyvinylpyrrolidone (US 4192827).

At present preferred polymer is a kind of hydrophilic polyurethane foam prepolymer, applies then with its aqueous solution and reacts on the spot.This foamed polyurethane can use the urethane prepolymer of any kind of, makes the sort of of reticular opening foam body after promptly being generally used for reacting.Preferred hydrophilic urethane prepolymer for example comprises the end capped polyoxy alkylidene ether of Carbimide., comprises the polyoxyethylene polyol prepolymer.The prepolymer that is suitable for is indicated in US 4137200(Cross Linked Hydrophilic Foams and Method); US 4209605(Process for producing Shaped Polyurethane Hydrogel Articles); US 2993013(Cellular Polyuret hane and Method of Preparing Same); US 3805532.The conventional method of preparation prepolymer is indicated in J.H.Saunders and K.C.Frisch in Polyurethanes Chemistry and Technology, Interscience Publishers, John Wiley ﹠amp; Sons, New York, Vol., XVI, Part, 2, High Polymer Series, " Foam Systems ", pp.7-26, and " Procedures for the Preparation of Prepolymers ", p.26 etc.

Preferred prepolymer is TREPOL ^TMPolyurethane prepolymer is by Twin Rivers Engineering, Route ^#27, Boothbay, Maine 04537 supply.TREPOL ^TMPrepolymer is a kind of polyisocyanate blocked Polyethylene Glycol, wherein have to be less than 6% unreacted NCO group, the component degree of functionality be 2 or below.In another program, can use HYPOL 3000 ^TMPrepolymer.HYPOL 3000 ^TMBe a kind of polyisocyanate blocked polyoxyethylene polyol prepolymer, the reactive functional group degree of this prepolymer molecule is supplied by W.R.Grace Company of New York greater than 2.

Contain aqueous phase at this and can add surfactant with reconciliation statement surface tension and adjusting wettability.The result can make and become hydrophilic structure and flow in the space of cotton thread structure.Surfactant for example has: Schercopol OMS-N, and this is a kind of single oleoyl ammonia monoethanolamine disodium sulfosuccinate, supplier Scher Chemicals, Inc., Industrial West, Clifton, New Jersey 07012; PPG 1025, and this is a kind of polypropylene glycol surfactant; Pluronic F68 or P75, this is a kind of non-ionic surface active agent, is the block copolymer of oxirane and expoxy propane, the BASF supply; Alcolec HS-3, this is lecithin and sulfonation glyceride aqueous solution active compound, supplier American Lecithin Company, 32-34 61st Street, Woodside, Long Island, New York 11377.

This hydrophilicity prepolymer is contained water and is activated when mixing, polymerization takes place.The point important to the present invention, this contains water and prepolymer blending ratio and is enough to make mixture to reach suitable operated viscosity.In the scheme of using the ammonia ester, this ratio is generally at about 6: 1 to 400: 1.This solution constitutes a kind of flowable early stage liquid polyurethane, after they are attached on the yarn, just solidifies in the original place.Described early stage foams deposit to out on rare woven cellulose line, and excessive water penetrates fiber.Use above-mentioned about 6: 1 to 400: the hydrophilic urethane prepolymer moisture relative prepolymer of 1() can obtain such coated product, and they have very high-hydroscopicity, and meets physical property requirements such as ruggedness, subduing property and drapability.The water content height of this mixture does not produce foam substantially in the time of on thin film paint cotton cloth.The resulting polymers coating does not still have abscess independent, that clearly define with cotton fabric tool absorbability as a result.

Excessive water in polymerization reaction mixture can be regulated viscosity, and this solution is easy on the line of paint cotton cloth.Because automated production is carried out in the permission of the rheological equationm of state of this solution.Excessive water also helps to disperse liberated heat, and the temperature of inhibitory reaction.Excessive water also can guarantee whole available isocyanates site is all reacted away, and makes the resulting composition avirulence.

The US-A-013255 of co-applications proposes a kind of method of making composite, uses equipment shown in Figure 5.Use the cotton cloth material of early stage foamed resin of the present invention can use this kind device fabrication.In the method, the gauze of this aqueous resins coating can be flooded by resin to guarantee this net material, and definite polymer occupy the degree in zone between the fiber stitching through squeezing.Squeeze at scalable roll gap place at pressing device 40, or squeezing between the parallel belts up and down, or squeeze (not shown) in the conveyer belt of similar functions.Another way can be squeezed between the two halves die, and this mould can be by the shaped design moulding (not shown) of this composite material surface.Generally, squeezing degree height can reduce the relative quantity (low foam density) of early stage foamed resin and trend towards preserving better interfibrous space.

Fig. 5 is the sketch map that the present invention carries out each step device therefor.Woven cotton cloth fibrous material 30 is from feed roller 32 debatchings, and advances with horizontal direction.Each sheet material 30 is all passed through aggregate device 33.Liquid polyurethane foamed resin or other hydrophilic resins of blending are sent from blending machine/dispenser 34, and are assigned to the whole surface of material 30.Along with width of cloth material advances, the early stage resin of this flowability liquid promptly penetrates into material 30.

The material 36 of coating resin is squeezed by pressing device 40, and this device comprises a pair of pressure roller 41 and 22 as shown, and has adjustable roll gap.Pressing device 40 further further distributes resin and makes it evenly within material 36, and by squeeze this material determine wherein with the relative quantity of early stage resin, and Density Distribution, thus the control foam body occupies regional degree between the stitching of fiber.

Make then and pass through solidification equipment 50, finish polyreaction, and the ammonia ester is solidified at this place by resin-coated material.The roller (not shown) that air heater 52 or heating can be arranged in the solidification equipment 50, or the both uses.Solidification equipment 50 also can comprise air exhauster system 54.This polymer reaction and coating process can carry out in room temperature.Among the curing or afterwards, composite 55 can pass through separate roller 56, the composite 55 that this roller assists to keep multi-disc in solidification process separately.

After the curing, composite 55 can and be delivered to takers-in 60 by a pair of driven roller 58,59.Driven roller 58,59 can make multiwalled composite 55 merge becomes the monolithic that the multilamellar gauze is arranged.

Cotton cloth can be handled after the debatching on storing roller at it, or can handle with strip.Also can immerse gauze in the polymer and rub rub, roll-in or hang-up dry.After liquid-carrier all being proposed or evaporate (can carry out drying at room temperature or oven drying), solidified composite can be cut into certain size or rolling and store.

Can further understand the present invention by following indefiniteness embodiment, these are to implement the preferred method of the present invention at present.

In the laboratory mixer, deionized water, polyurethane foam prepolymer and various superficiality agent are mixed into agent.The surgical cloth (Kendall) that compresses package is immersed in this mixed liquor, then debatching immediately and air-dry in the room temperature suspension.Each sample is estimated the ability that its fiber and cotton residue remain on original position, and measure opening rare structure and whether keeping of gauze.The mensuration of fiber and resin wear amount is, handled gauze to 3 * 3 inches one and has been placed on the filter glass, clamps this sheet and rubs 10 times with two palms, and all loose fibres and resin are fallen on the black surface.With the naked eye check then and count the granule that comes off, without microscope.

In practicality, the effect test that this gauze is handled is test bar to be put in the boiling water and under the boiling situation strip waved rock.Gained liquid is by a particle collector, for example Coulter enumerator.Can record the accurate distribution situation of fiber and resin in this way, because every kind all has a certain size scope.List test result below:

Table 1

Example EG/ H ₂O F68 TREPOL ^TMFibre resin

Numbering HS-3 comes off

10 400 01 is a lot

2 10.05 56.9 021 is a lot

3 10.95 56.9 05 a little is a lot

4 12 88 0 7 0 80

5 12 88 0 3 6 80

The sealing of 60 73.5 1.5 10 yarn eyes

7 0 88.2 1.8 10 7 30

8 0 93.1 1.9 5 18 80

9 0 99.5 0.5 30 0 3

10 0 99.5 0.5 12 0 0

11 0 99.5 0.5 12 0 20

12 0 99.5 0.5 5 1 2

13 0 99.5 0.5 2 8 30

14 0 99.5 0.5 1 2 25

15 0 99.5 0.5 0.5 16 20

16 0 99.5 0.5 0 58 50

17 untreated gauze as many as are countless

EG/HS-3 is two kinds of surfactant mixtures: Emulgade 100NI, and Henkel Corporation supply, this is the mixture of the pure and mild ceteaseth-20 of cetearyl; Also have Alcolec HS-3, this is lecithin and the active compound of sulfonation glyceride in aqueous solution, American Lecithin Company supply.Emulgade and HS-3 are made into 2.5% aqueous solution, mix to becoming the solution (or aqueous solution of 5%EG/HS-3) that contains 95% water together then.F68 is Pluronic F68, this is oxirane and propylene oxide block copolymer non-ionic surface active agent, the BASF supply.TREPOL ^TMBe the end capped Polyethylene Glycol of toluene-2,4-diisocyanate, its effective unreacted NCO group is less than 6%, and the component degree of functionality is 2 or littler.Be that Route 27, Boothboy, Maine, 04537 by Twin Rivers Engineering supply.

Data show in the table I, use surfactant such as F68 can significantly reduce the amount of come off fiber and resin.Example 2 and 3 shows, changes the prepolymer consumption, uses at the same time under the EG/HS-3 situation resin wear amount is not had influence.In fact, shown in example 4 and 5, the amount that changes the F68 surfactant does not separately influence the resin wear amount.

Example 6,7,8 shows that when different water compared polymer ratio, the low concentration prepolymer produced " the yarn eye of sealing ", that is the zone is filled between the stitching of gauze.Example 9 to 16 shows variation prepolymer TREPOL ^TMTo the influence of the ratio of water to fiber and resin wear.These examples show, optimize proportioning i.e. 99.5 parts of water, 0.5 part of surfactant F68 and 12 parts of prepolymer TREPOL when adopting ^TMThe time, can reach fiber and resin wear and be zero.Example 11 is that with the difference of example 10 gauze after the former adopts air blast by coating is opened the gauze mesh.Example 11 shows that it is the suboptimum person of choosing that this additional treatment step makes the gauze treatment effect.

The present invention can also implement by other concrete forms.

Claims (14)

1, a kind of durable, in fact not lint hair, water absorption, can dangle, the nontoxic composite that can be used for wound dressing, comprising:

A kind of tool warp yarn and weft threads open rare weaving fiber cellulose fiber material; And

Apply one deck hydrophilic polymer film on described yarn, the thickness of film is enough to make and stays the space of opening on the material that is made into by described yarn.

2, by the composite of claim 1, wherein said cellulosic fibre material is woven cotton cloth.

3, by the composite of claim 1, wherein said polymer is a kind of polyurethane foam prepolymer, and applies up with the aqueous solution form.

4, by the composite of claim 3, wherein said prepolymer is by the end capped Polyethylene Glycol of toluene-2,4-diisocyanate.

5, by the composite of claim 1, wherein also contain a kind of surfactant.

6, by the composite of claim 5, wherein said surfactant is poly-(oxygen ethylidene-oxygen propylidene) polyhydric alcohol of a kind of hydrophilic.

7, by the composite of claim 3, the water of wherein said aqueous solution to the polymer ratio scope for being about 6: 1 to about 400: 1.

8,, it is characterized in that its water absorbability can be at least two times of coating cellulose fibrous material not by the composite of claim 7.

9,, it is characterized in that described water absorbability can be about 300% to about 450% scope by the composite of claim 8.

10, by the composite of claim 1, wherein said hydrophilic polymer is a poly(ethylene oxide).

11, by the composite of claim 10, wherein said hydrophilic polymer also contains carboxymethyl cellulose.

12, by the composite of claim 1, wherein said polymer is a polyvinylpyrrolidone.

13, a kind ofly make durable, the method for lint hair, water absorption, the wound dressing material that can dangle not in fact, may further comprise the steps:

Prepare a kind of coating aqueous solution, wherein contain dissolved hydrophilicity prepolymer, and its viscosity and surface tension are suitable for making described solution absorbs on cotton fiber;

This coating solution paint is opened on the warp and parallel of rare woven cotton gauze, formed liquid coating continuous, coating cotton thread thereon;

With this prepolymer cures, on described warp and parallel, form adherent hydrophilic polymer coating, keep the rare weaving structure of opening of this gauze simultaneously, and the particulate matter on the described gauze is sealed.

14, by the method for claim 13, wherein said applying comprises the step of exerting pressure in the coating step, force described pre-polymer solution to enter in the space that cotton fiber limited of described yarn.

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