CA2186726A1 - Thermoplastic hydrogel impregnated composite material - Google Patents
Thermoplastic hydrogel impregnated composite materialInfo
- Publication number
- CA2186726A1 CA2186726A1 CA002186726A CA2186726A CA2186726A1 CA 2186726 A1 CA2186726 A1 CA 2186726A1 CA 002186726 A CA002186726 A CA 002186726A CA 2186726 A CA2186726 A CA 2186726A CA 2186726 A1 CA2186726 A1 CA 2186726A1
- Authority
- CA
- Canada
- Prior art keywords
- composite material
- polymer
- wound
- thermoplastic hydrogel
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 23
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229920000742 Cotton Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 19
- 229920000578 graft copolymer Polymers 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- -1 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 229920006030 multiblock copolymer Polymers 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 229920002959 polymer blend Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 229920001390 poly(hydroxyalkylmethacrylate) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 238000010128 melt processing Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 206010052428 Wound Diseases 0.000 description 54
- 208000027418 Wounds and injury Diseases 0.000 description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 210000000416 exudates and transudate Anatomy 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXSKAZFMTGADIV-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)propoxy]ethanol Chemical compound OCCOCCCOCCO KXSKAZFMTGADIV-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- 102100034033 Alpha-adducin Human genes 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000799076 Homo sapiens Alpha-adducin Proteins 0.000 description 1
- 101000693243 Homo sapiens Paternally-expressed gene 3 protein Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229930182816 L-glutamine Natural products 0.000 description 1
- 102100025757 Paternally-expressed gene 3 protein Human genes 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 101000629598 Rattus norvegicus Sterol regulatory element-binding protein 1 Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002652 polymer substitute Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000010572 single replacement reaction Methods 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000000472 traumatic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- A61F13/01017—
-
- A61F13/01042—
Abstract
A composite material for wound dressings having a fibrous wound-contacting substrate, such as cotton gauze, impregnated with a thermoplastic hydrogel forming polymer and methods of making the same.
Description
THERMOPLASTIC HYDROGEL IMPREGNATED COMPOSITE MATERIAL
The present invention is directed to a composite material suitable for application as a wound dressing. The composite material includes a fibrous wound-contacting substrate, such as a cotton gauze, impregnated with a thermoplastic hydrogel forming 5 polymer. The composite material is highly absorbent and does not stick to the wound surface.
BACK~;ROUND OF THE INVENTION
Conventional materials for use as wound dressings, such as cotton gauze, suffer from a number o disadvantages. For 10 example, cotton gauze tends to stick to the wound during the healing process. Removal of the wound dressing under these circumstances destroys tissue and is uncomfortable for the patient. To reduce sticking and optimize would healing, the wound dressing must be replaced often.
Another disadvantage of using cotton gauze in wound dressings arises from the construction of the gauze material.
Cotton gauze is manufactured from twisted cotton fiber which is cleaned, bleached and sterilized. During the cleaning and bleaching process, the thread is exposed to chemical treatments and becomes associated with leftover starch, proteins, casein and resins. These materials, plus small fibers or lint, often disassociate from the cotton gauze and contaminate the wound.
In some cases, particularly during surgery, serious infections can result.
Efforts have been made to overcome the disadvantages associated with gauze-type wound dressings by coating or impregnating the gauze material. Romano Cali, U.S. Patent No.
4,748,976 discloses a wound dressing in which a cotton ~iabric is impregnated with a cosmetic preparation held in an oil or a grease medium. Nigel J. Brassington et al., U.S. Patent No.
SUBSTITUTE SHEET (RULE 26) WO 95/26699 . ~ ' i3~
- 2 - 2t86726 4,838,253 disclose a wound dressing comprised of a cotton gauze coated with a tacky silicone gel or a non-tacky silicone elastomer .
Paul F. Hermann et al., U.S. Patent No. 5,135,472 disclose 5 a composite gauze material coated with a hydrophilic polymer.
The polymer is stated to bind with the hydroxyl groups of the gauze material. Such polymers include a polyurethane foam prepolymer, and polymers of ethylene oxide, carboxymethyl cellulose or polyvinylpyrrolidone.
lo Despite these efforts there is a continuing need to develop composite materials for use as wound dressings which are highly absorbent, do not stick to the wound and reduce or eliminate infiltration of fibers and by-products of manufacture into the wound .
SU1~ARY OF THE Il~IVENTION
The present invention is directed to a composite material particularly suited as a wound dressing. The composite material is comprised of a fibrous wound-contacting substrate, the most common example of which is cotton gauze. The substrate i5 20 impregnated with a layer of a thermoplastic hydrogel forming polymer (hereinafter "the hydrogel polymer"). Such polymers include A-B-A block copolymers, multiblock copolymers, graft copolymers and polymer blends each incorporating a hydrophilic component - and a hydrophobic component. The hydrogel polymer 25 exhibits microphase separation of the hydrophobic component which makes the hydrogel polymer water insoluble, yet water-swellable, and therefore highly absorbent.
The substrate7hydrogel polymer composite resulting from impregnation of the substrate with the hydrogel polymer is 30 initially dry. Upon the upta~:e of exudate from the wound, the dry composite becomes slippery or "slimy" and thereby does not entrap tissue so that the wound dressing does not stick to the wound during healing. Consequently upon removal of the wound SUaSTlTUTE SHEET (RULE 26) W0 95/26699 r .
67 ~ 6 dressing, there is minimal or no injury to the healing tissue.
Further, due to increased absorptive capacity, the composite material of the present invention may be retained on the wound for longer periods of time than conventional cotton gauze. Fewer 5 changes of the wound dressing reduces material costs and reduces the time needed by medical personnel to administer to a patient's wound .
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a composite material 10 adapted for use as a wound dressing in which a fibrous wound-contacting substrate, impregnated with a thermoplastic hydrogel-forming polymer, is placed in direct contact with an open wound.
Examples of such substrates include pure cotton fabric, cotton gauze, and open weave cellulose fiber materials such as those disclosed in Romano Cali, U.S. Patent No. 4,748,976; Nigel J.
Brassington et al., U.S. Patent No. 4,83a,253; Paul F. Hermann et al., U.S. Patent No. 5,135,472; and Richard B. Ponder et al., "Gauzes and Related Dressings", OstomY/Wound Manaqement, Vol. 39, No. 5, pp. 48-60 ~June, 1993), each of which is incorporated herein by reference. Synthetic materials such as rayon, rayon/polyester blends, Dacron and the like may also be used.
The wound-contacting substrate is impregnated with the hydrogel polymer. The hydrogel polymers having application in the present invention include A-B-A block copolymers, multiblock copolymers, graft copolymers and polymer blends each incorporating a hydrophilic and a hydrophobic component. The hydrogel polymers which are particularly advantageous in the present invention are those exhibiting microphase separation with a hydrophilic/ hydrophobic domain system.
Such hydrogel polymers are thermoplastic. Accordingly, they are soluble in conventional organic solvents and soften upon the application of heat. The hydrogel polymers are distinguished from thermosetting polymers which are insoluble in organic SUBSTITUTE SHEET (RULE 26) W095l26699 r~l~u..,'. ~ '--_ 4 _ ;~ I 86726 solvents and do not melt upon heating. rhe hydroqel polymers employed in the present invention may therefore be prepared separately, puri~ied, and then impregnated into the substrate.
Thermoplastic hydrogel polymers for use in the present invention 5 are disclosed in, for example, "~ater-Soluble Polymers", K.R.
Shah in S.W. Shalaby et al., ACS SVmDosium Series, Vol. 67, Chapter 30, PP. 469-483 (1991), incorporated herein by reference.
The morphology of the hydrogel polymers is characterized by a hydrophilic or water soluble continuous phase and a hydrophobic 10 or water insoluble dispersed phase, which prevents the continuous phase from dissolving in water. Thus, when the hydrogel polymer is placed in an aqueous environment, it absorbs water and swells to an equilibrium volume, but does not dissolve in water. More specifically, the hydrogel polymers have an equilibrium water 15 content, defined as the percentage by weight of water absorbed, based on the weight of the hydrated sample, of up to about 99%, typically from about 40 to 99%.
The polymer systems which exhibit hydrophilic-hydrophobic domains include, but are not limited to (a) A-B-A block 20 copolymers, (b) multiblock copolymers, (c) graft copolymers and (d) polymer blends, each having a hydrophilic and a hydrophobic component .
The A-B-A type block copolymers are those wherein the A
block is hydrophobic and the B block is hydrophilic. Examples 25 of hydrophobic blocks include polystyrene, poly(methyl methacrylate), polyacrylonitrile, polyesters, polyamides, and the like. Examples of hydrophilic blocks include polyethylene oxide, poly (hydroxyalkyl methacrylate) and derivatives thereof, polyacrylamide, poly(N-vinyl lactam), polyacrylic acid, and the 30 like, Some of the polymeric compositions which fall under this category include: copolymers of styrene and 2-hydroxyethyl methacrylate reported by ~. Okano, et al.; J. ADD1. PolYm. Sçi., Vol. 22, p. 369 (1978~ and J. BiQmed. Mat. Research~ Vol. 15, p. 393 (1981), each of which is incorporated herein by reference;
35 triblock copolymers based on polyethylene oxide and lactic acid SUBSTITUTE SHEET lRULE 26) Wo gsl26699 '`~d~ 5- 2~86726 and trimethylene carbonate copolyester as disclosed in L. Rosati et al., PolYm. Mat. sci. ~ Encl., Am. Chem. Soc., PrePrints, Vol.
59, p. 516 (1988); triblock copolymer of poly(hydroxyalkyl L-glutamine) and polyethylene oxide as disclosed in Am. Chem. Soc., Symp., Ser., No. 520 (1992). Methods of preparing A-B-A type block copolymers for use in the present invention are also disclosed in these publications, each o f which is incorporated herein by reference.
The multiblock copolymers have alternating sequences of hydrophilic and hydrophobic polymeric blocks as described above for the A-B-A type block copolymers. Examples of these copolymers include copolymers of polyacrylonitrile and hydrophilic derivatives of acrylic acid as disclosed in V.A. Stoy et al., U.S. Patent No. 4,095,877 and V.A. Stoy, U.S. Patent No.
4, 369, 294, and polyethylene oxide/lactic acid copolymers as disclosed in D. Cohn, et al., J. Biomed. Mat Res., Vol. 22, p.
993 (1988). Methods of preparation of the multiblock copolymers for use in the present invention are also disclosed in the publications, each of which is incorporated herein by reference.
The graft copolymers comprise hydrophilic main chain polymer and hydrophobic polymeric grafts. Hydrophobic and hydrophilic structures for the graft copolymers are as described above for the A-B-A type block copolymers. ~xamples of such graft copolymers include poly(N,N-dimethylacrylamide-g-styrene) as disclosed in R. Milkovich et al., U.S. Patent No. 4,085,168; and poly(2,3-dihydroxypropyl methacrylate-g-styrene) as disclosed in T. Tsukahara, et al., PolYm. J, Vol. 19, p. 1033 (1987). Methods of prepar~tion of the graft copolymers for use in the present invention are also disclosed in the publications, each of which is incorporated herein by reference.
The polymer blends are preferably blends of two polymers, one of which is a homopolymer or a copolymer of an N-vinyl lactam and the other is an acrylic copolymer containing a small SU~STITUTE SHEET (RULE 26) WO95126C99 ~ 5 ~ --proportion of acidic groups as disclosed in K. Shah, [I.S. Patent No. 4,300,820, incorporated herein by reference which also discloses methods of forming the polymer blends.
The copolymers including A-B-A block, multiblock and graft copolymers and the polymer blends employed in the present invention may be formed as a solution or may be melt processed through an extruder to impregnate the hydrogel polymer into the substrate .
For example, a graft copolymer of N,N,dimethylacrylamide and the polystyrene-based macromonomer may be prepared by free radical initiated solution copolymerization. The starting materials are reacted in the presence of a polymerization solvent, such as ethyl acetate, ethanol, methyl ethyl ketone, 2cetone, tetrahydrofuran, mixtures thereof and the like, and a polymerization catalyst (e.g. asobisisobutyronitrile) at a reaction temperature in the range of up to about 80'C.
The resulting solution containing the copolymer is then optionally purif ied to remove unreacted monomer and other impurities. For example, the copolymer solution may be zo precipitated with a non-solvent, such as an ether compound, in particular diethyl ether, at a weight ratio of about l:l to l:lo, preferably about 1: 2 . The resulting precipitated copolymer is separated, and dried and then reconstituted in solution by adding additional solvent.
The copolymer containing solution may be combined with a conventional plasticizer such as polyethylene glycol (e.g. PEG-400), glycerine, mixtures thereof and the like to form a solution for impregnating the substrate.
The solution typically contains up to 40% by weight, preferably from about 2 to 20% by weight, of the hydrogel polymer. The hydrogel polymer may optionally contain up to about 60% by weight, preferably form about 15 to 60~ by weight of the plasticizer based on the weight of the plasticized hydrogel SU~STIT=E SHEET (RULE 26) S I
~ Wo 9S/26699 2 ~ ~6726 polymer. The balance of the solution is comprised of an organic solvent, typically from about 60 to 96% by weight of the solution .
The copolymer containing solution is applied to the wound-contacting substrate in any manner capable of uniformly impregnating the substrate. Dipping and spraying are two conventional methods for impregnating the solution although dipping is preferred. In this method, the wound-contacting substrate is dipped into a bath containing the solution. The impregnated substrate is then removed from the bath and allowed to dry. During the drying step, the solvent evaporates leaving the plasticized thermoplastic hydrogel on the substrate.
Alternatively, the hydrogel polymer, optionally with a plasticizer, may be melt processed through an extruder to impregnate the hydrogel polymer into the substrate. The hydrogel polymer in the form of a dry powder is placed into an extruder and heated. The melted hydrogel polymer is then formed into a sheet atop the substrate. The composite is then compressed until the hydrogel polymer impregnates the substrate.
The extent to which the hydrogel polymer is impregnated into the substrate is selected depending on the desired absorption capabilities of the wound dressing. Generally, the greater the amount of the hydrogel polymer impregnated, the greater the absorption capability of the wound dressing and the longer the wound dressing may be retained on the wound. The extent of impregnation is related to the dry weight of the applied hydrogel polymer per unit weight of the wound-contacting substrate. For most standard substrates, (e.g. cotton gauze) the dry weight of the impregnated polymer is in the range of from about 50 to 500%
by weight of the cotton gauze, preferably from about 60 to 150%
by weight.
The composite material of the present invention can absorb moisture up to about 15 times its weight, depending on the relative weight of the hydrogel polymer, without being dissolved away from the wound-contacting substrate. The hydrogel polymer SUBSTITUTE SHEET (RULE 26) .. ..... .. . .. .. . . . . . . . . . _ _ ~
'O:~Ql W095/26699 _ I~", 8 - 2 ~ 8 6 7 2 ~
is essentially in a dry state on the wound-contacting substrate and becomes slippery as it absorbs moisture. 51ippery or lubricous substrates serve the function of preventing adhesion of the substrate to the tissue of the wound. When the substrate is removed, the material comprising the substrate such as gauze is easil~ separated from the tissue without damaging the wound or inflicting paIn on the patient. The impregnation of a gauze like fibrous wound contacting substrate in accordance with the invention prevents shedding of lint and other particulate matter into the wound.
In accordance with another aspect of the claimed invention, the composite material containing the hydrogel polymer impregnated therein may have optionally thereon a material which improves handling or lubricity of the composite material. The preferred type of material for this purpose is a water-soluble biocompatible material in the form of fine particles (e.g. a powder). Such materials include gelatin, pectin, dextran and sodium carboxymethylcellulose. The amount of such materials should be sufficient to eliminate any residual tackiness o~ the composite material.
The composite material as described above may be incorporated into a variety of wound dressings including top dressings for superficial-type wounds as well as packing dressings for chronic and traumatic wounds. Examples of the former type of wound dressings are disclosed, for example, in U.S. Patent Nos. 3,425,412 and 4,513,739 and T).S. Patents disclosed therein, each of which is incorporated herein by reference. Common wound care products are also disclosed in Richard B. Ponder, et al. publication previously mentioned.
Composite materials in accordance with the present invention absorb significantly more exudate from a wound than conventional uncoated gauze-type materials. By way of example, if a conventional wound dressing required replacement 3 to 4 times over the course of an eight hour nurses shift, a wound dressing of the present invention may require only a single replacement.
SUBSTIT~JTE SHEET ~RULE 26) ~0 95/26699 T ~
21 86726 ~
67 ml of ethyl acetate was charged into a four-mouth round bottom flask. 32.175g of N,N-dimethylacrylamide and 0.825g of polystryene methacrylate macromonomer having a number average 5 molecular weight of 13, 000 (manufactured by Sartomer) were added to the flask. 0 . 033g of azobisisobutyronitrile dissolved in 2 . 0 ml of ethyl acetate was slowly added to the mixture under constant stirring until a completely clear mixture was obtained.
The flask was placed in an ethylene glycol bath maintained 10 at 50 C for 60 minutes. The bath temperature was gradually raised to 80-C over 15 minutes and the contents of the flask continuously mixed over the next 120 minutes. Thereafter, the reaction w~s terminated by removing the flask from the bath and allowing the reaction mixture to cool.
The resulting solution containing the graft copolymer composed of 2 . 5~6 by weight of polystyrene methacrylate was combined with 200 ml of diethyl ether, whereupon the graft copolymer precipitated. The supernatant liquid was decanted and the graft copolymer residue washed with diethyl ether until the 20 washings were completely clear.
The purified graft copolymer was combined with 300 ml of ethyl acetate and 27g of polyethylene glycol (PEG-400 Aldrich Chemicals) and stirred until a homogenous solution was obtained.
The solution was cast over folded silicone coated release papers 25 and allowed to dry overnight. The sheets were then placed in a vacuum oven and dried overnight at room temperature followed by drying at 50-C for at least 5 hours.
The copolymer sheet was immersed in water for 24 hours. The fully hydrated graft copolymer was removed from the liquid, 30 weighed, dried at So C for 24 hours and then reweighed. The equilibrium water concentration (EWC~ of the hydrated copolymer was 97~ as shown in ~able 1.
SUeSTlTUTE SHEET (RULE 26) WO 95/26699 ~CTIUS95/03813~
~ ~'t'~ ~ 10 ~ 2186726 EX~MPLE *AMOUNT OF MACROMONO~ER EWC (%) IN THE GRAFT COPOLY~ER
% BY ~EIGHT) 2.5 97 2 5.0 95 3 10.0 91 4 20. 0 75 5 30.0 63 1 - Percentage by weight of water absorbed based on the weight of 10 the hydrated sample, EXAMPT,~ 2-5 Example l was repeated for each of Examples 2-5 except that the amount of the polystyrene methacrylate macromonomer in the graft copolymer was increased to 5.~, lO.0, 20.0 and 30.096 by 15 weight, respectively. The results are shown in Table 1.
As shown in Table 1 each of Examples 1-5 show significant water absorption. It is further shown that the amount of water absorption increases as the amount of the polystyrene methacrylate macromonomer in the graft copolymer decreases.
2 O EXAMP~ ~ 6--J3 20. 0 parts by weight of the hydrogel polymer formed in accordance with the method of Example 3 was dissolved in 63 . 6 parts by weight of acetone containing 16 . 4 parts by weight of PE6-400 to obtain a clear hydrogel solution.
A woven type I gauze was dipped into the hydrogel solution for a few seconds. The residual solution was removed by passing the gauze through a pair of rollers. The gauze was heated in an oven at 120'C for three minutes to evaporate the solvent.
A 2" x 4" sample of the gauze (Example G) was placed on a piece of wet sponge in a chamber having a temperature Qf 40-C and a relative humidity o~ 75%. The weight of the sample was SUBSTITUTE SHEET (RULE 26) -WO 95/26699 r~
r ~ 1 8 6 7 2 6 ~, .
measured every 5 minutes during the first 30 minutes and every 30 minutes for the next two hours until saturation.
The amount of water absorbed by the sample was calculated as follows:
wate~ a~sorption _ wt(time) - wtl . .
at designated time ~ unit a~ea wt (time) = weight of the sample at the designated time wtl = dry weight of the sample before being placed on the sponge Two additional samples (Examples 7 and 8) were prepared and tested in the same manner as Example 6 except that the dipping 10 and drying process was repeated to increase the amount of the hydrogel polymer impregnated in the gauze material as indicated in Table 2.
WATER ABSORPTION
G/ ~z ~Y DROGEL
POLYMER AMOUNT
EXAMPLE ~EIGHT2 OF PEG3 5 MIN. 25 MIN.
15 6 30% 45% 61 63 753% 45% go 100 8639~ 45% 137 128 2 _ Based on the weight of the non-impregnated gauze.
3 - Based on the combined weight of the hydrogel polymer and PEG.
As shown in Table 2, Examples 6-8 provide significant water absorption in just 5 minutes and retain the absorbed water.
Table 2 further shows that increasing the weight of the hydrogel polymer increases the amount of water absorption of the gauze material .
SUBSTITUTE SHEET (RULE 26) r~
wo 9S/266gJ
- 12 - 2 ~ 8 67 2 6 EXAMpT.F g A sample of a hydrogel polymer impreynated qauze was prep2red in the same manner as Example 6. After drying of the hydrogel polymer, a small amount of sodium carboxymethyl-cellulose powder (6-30 mg/in2) was sprinkled onto both sides of the gau z e .
The thus treated sample was tested for water absorption in the same manner as Example 6. The test results showed that the sample (Example 5) exhibited a slight increase in the rate of water absorption over Examples 6-8. There was also observed a reduction in the adhesiveness of the surface of the gauze material .
t:~OMPARATI~'E EXAMPr,F:
The same type of gauze material employed in Examples 1-8 without tlle hydrogel polymer of the present invention was tested for water absorbency in the same manner as Examples 1-8. After 5 minutes, the amount of water absorbed was about 37 g/m2. After 25 minutes, the amount of water absorbed decreased to about 27 9/m2 ~
As shown in the Examples, the water absorbing capability of wound dressings impregranted with the hydrogel polymer in accordance with the present invention significantly exceeds the water absorbing capability of conventional gauze. In addition, the wound dressings of the present invention do not stick to the wound because, once exudate is absorbed, the wound dressing becomes slippery and does not adhere to tissue during the wound healing process.
SU9STITUTE SHEET ~RULE 26)
The present invention is directed to a composite material suitable for application as a wound dressing. The composite material includes a fibrous wound-contacting substrate, such as a cotton gauze, impregnated with a thermoplastic hydrogel forming 5 polymer. The composite material is highly absorbent and does not stick to the wound surface.
BACK~;ROUND OF THE INVENTION
Conventional materials for use as wound dressings, such as cotton gauze, suffer from a number o disadvantages. For 10 example, cotton gauze tends to stick to the wound during the healing process. Removal of the wound dressing under these circumstances destroys tissue and is uncomfortable for the patient. To reduce sticking and optimize would healing, the wound dressing must be replaced often.
Another disadvantage of using cotton gauze in wound dressings arises from the construction of the gauze material.
Cotton gauze is manufactured from twisted cotton fiber which is cleaned, bleached and sterilized. During the cleaning and bleaching process, the thread is exposed to chemical treatments and becomes associated with leftover starch, proteins, casein and resins. These materials, plus small fibers or lint, often disassociate from the cotton gauze and contaminate the wound.
In some cases, particularly during surgery, serious infections can result.
Efforts have been made to overcome the disadvantages associated with gauze-type wound dressings by coating or impregnating the gauze material. Romano Cali, U.S. Patent No.
4,748,976 discloses a wound dressing in which a cotton ~iabric is impregnated with a cosmetic preparation held in an oil or a grease medium. Nigel J. Brassington et al., U.S. Patent No.
SUBSTITUTE SHEET (RULE 26) WO 95/26699 . ~ ' i3~
- 2 - 2t86726 4,838,253 disclose a wound dressing comprised of a cotton gauze coated with a tacky silicone gel or a non-tacky silicone elastomer .
Paul F. Hermann et al., U.S. Patent No. 5,135,472 disclose 5 a composite gauze material coated with a hydrophilic polymer.
The polymer is stated to bind with the hydroxyl groups of the gauze material. Such polymers include a polyurethane foam prepolymer, and polymers of ethylene oxide, carboxymethyl cellulose or polyvinylpyrrolidone.
lo Despite these efforts there is a continuing need to develop composite materials for use as wound dressings which are highly absorbent, do not stick to the wound and reduce or eliminate infiltration of fibers and by-products of manufacture into the wound .
SU1~ARY OF THE Il~IVENTION
The present invention is directed to a composite material particularly suited as a wound dressing. The composite material is comprised of a fibrous wound-contacting substrate, the most common example of which is cotton gauze. The substrate i5 20 impregnated with a layer of a thermoplastic hydrogel forming polymer (hereinafter "the hydrogel polymer"). Such polymers include A-B-A block copolymers, multiblock copolymers, graft copolymers and polymer blends each incorporating a hydrophilic component - and a hydrophobic component. The hydrogel polymer 25 exhibits microphase separation of the hydrophobic component which makes the hydrogel polymer water insoluble, yet water-swellable, and therefore highly absorbent.
The substrate7hydrogel polymer composite resulting from impregnation of the substrate with the hydrogel polymer is 30 initially dry. Upon the upta~:e of exudate from the wound, the dry composite becomes slippery or "slimy" and thereby does not entrap tissue so that the wound dressing does not stick to the wound during healing. Consequently upon removal of the wound SUaSTlTUTE SHEET (RULE 26) W0 95/26699 r .
67 ~ 6 dressing, there is minimal or no injury to the healing tissue.
Further, due to increased absorptive capacity, the composite material of the present invention may be retained on the wound for longer periods of time than conventional cotton gauze. Fewer 5 changes of the wound dressing reduces material costs and reduces the time needed by medical personnel to administer to a patient's wound .
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a composite material 10 adapted for use as a wound dressing in which a fibrous wound-contacting substrate, impregnated with a thermoplastic hydrogel-forming polymer, is placed in direct contact with an open wound.
Examples of such substrates include pure cotton fabric, cotton gauze, and open weave cellulose fiber materials such as those disclosed in Romano Cali, U.S. Patent No. 4,748,976; Nigel J.
Brassington et al., U.S. Patent No. 4,83a,253; Paul F. Hermann et al., U.S. Patent No. 5,135,472; and Richard B. Ponder et al., "Gauzes and Related Dressings", OstomY/Wound Manaqement, Vol. 39, No. 5, pp. 48-60 ~June, 1993), each of which is incorporated herein by reference. Synthetic materials such as rayon, rayon/polyester blends, Dacron and the like may also be used.
The wound-contacting substrate is impregnated with the hydrogel polymer. The hydrogel polymers having application in the present invention include A-B-A block copolymers, multiblock copolymers, graft copolymers and polymer blends each incorporating a hydrophilic and a hydrophobic component. The hydrogel polymers which are particularly advantageous in the present invention are those exhibiting microphase separation with a hydrophilic/ hydrophobic domain system.
Such hydrogel polymers are thermoplastic. Accordingly, they are soluble in conventional organic solvents and soften upon the application of heat. The hydrogel polymers are distinguished from thermosetting polymers which are insoluble in organic SUBSTITUTE SHEET (RULE 26) W095l26699 r~l~u..,'. ~ '--_ 4 _ ;~ I 86726 solvents and do not melt upon heating. rhe hydroqel polymers employed in the present invention may therefore be prepared separately, puri~ied, and then impregnated into the substrate.
Thermoplastic hydrogel polymers for use in the present invention 5 are disclosed in, for example, "~ater-Soluble Polymers", K.R.
Shah in S.W. Shalaby et al., ACS SVmDosium Series, Vol. 67, Chapter 30, PP. 469-483 (1991), incorporated herein by reference.
The morphology of the hydrogel polymers is characterized by a hydrophilic or water soluble continuous phase and a hydrophobic 10 or water insoluble dispersed phase, which prevents the continuous phase from dissolving in water. Thus, when the hydrogel polymer is placed in an aqueous environment, it absorbs water and swells to an equilibrium volume, but does not dissolve in water. More specifically, the hydrogel polymers have an equilibrium water 15 content, defined as the percentage by weight of water absorbed, based on the weight of the hydrated sample, of up to about 99%, typically from about 40 to 99%.
The polymer systems which exhibit hydrophilic-hydrophobic domains include, but are not limited to (a) A-B-A block 20 copolymers, (b) multiblock copolymers, (c) graft copolymers and (d) polymer blends, each having a hydrophilic and a hydrophobic component .
The A-B-A type block copolymers are those wherein the A
block is hydrophobic and the B block is hydrophilic. Examples 25 of hydrophobic blocks include polystyrene, poly(methyl methacrylate), polyacrylonitrile, polyesters, polyamides, and the like. Examples of hydrophilic blocks include polyethylene oxide, poly (hydroxyalkyl methacrylate) and derivatives thereof, polyacrylamide, poly(N-vinyl lactam), polyacrylic acid, and the 30 like, Some of the polymeric compositions which fall under this category include: copolymers of styrene and 2-hydroxyethyl methacrylate reported by ~. Okano, et al.; J. ADD1. PolYm. Sçi., Vol. 22, p. 369 (1978~ and J. BiQmed. Mat. Research~ Vol. 15, p. 393 (1981), each of which is incorporated herein by reference;
35 triblock copolymers based on polyethylene oxide and lactic acid SUBSTITUTE SHEET lRULE 26) Wo gsl26699 '`~d~ 5- 2~86726 and trimethylene carbonate copolyester as disclosed in L. Rosati et al., PolYm. Mat. sci. ~ Encl., Am. Chem. Soc., PrePrints, Vol.
59, p. 516 (1988); triblock copolymer of poly(hydroxyalkyl L-glutamine) and polyethylene oxide as disclosed in Am. Chem. Soc., Symp., Ser., No. 520 (1992). Methods of preparing A-B-A type block copolymers for use in the present invention are also disclosed in these publications, each o f which is incorporated herein by reference.
The multiblock copolymers have alternating sequences of hydrophilic and hydrophobic polymeric blocks as described above for the A-B-A type block copolymers. Examples of these copolymers include copolymers of polyacrylonitrile and hydrophilic derivatives of acrylic acid as disclosed in V.A. Stoy et al., U.S. Patent No. 4,095,877 and V.A. Stoy, U.S. Patent No.
4, 369, 294, and polyethylene oxide/lactic acid copolymers as disclosed in D. Cohn, et al., J. Biomed. Mat Res., Vol. 22, p.
993 (1988). Methods of preparation of the multiblock copolymers for use in the present invention are also disclosed in the publications, each of which is incorporated herein by reference.
The graft copolymers comprise hydrophilic main chain polymer and hydrophobic polymeric grafts. Hydrophobic and hydrophilic structures for the graft copolymers are as described above for the A-B-A type block copolymers. ~xamples of such graft copolymers include poly(N,N-dimethylacrylamide-g-styrene) as disclosed in R. Milkovich et al., U.S. Patent No. 4,085,168; and poly(2,3-dihydroxypropyl methacrylate-g-styrene) as disclosed in T. Tsukahara, et al., PolYm. J, Vol. 19, p. 1033 (1987). Methods of prepar~tion of the graft copolymers for use in the present invention are also disclosed in the publications, each of which is incorporated herein by reference.
The polymer blends are preferably blends of two polymers, one of which is a homopolymer or a copolymer of an N-vinyl lactam and the other is an acrylic copolymer containing a small SU~STITUTE SHEET (RULE 26) WO95126C99 ~ 5 ~ --proportion of acidic groups as disclosed in K. Shah, [I.S. Patent No. 4,300,820, incorporated herein by reference which also discloses methods of forming the polymer blends.
The copolymers including A-B-A block, multiblock and graft copolymers and the polymer blends employed in the present invention may be formed as a solution or may be melt processed through an extruder to impregnate the hydrogel polymer into the substrate .
For example, a graft copolymer of N,N,dimethylacrylamide and the polystyrene-based macromonomer may be prepared by free radical initiated solution copolymerization. The starting materials are reacted in the presence of a polymerization solvent, such as ethyl acetate, ethanol, methyl ethyl ketone, 2cetone, tetrahydrofuran, mixtures thereof and the like, and a polymerization catalyst (e.g. asobisisobutyronitrile) at a reaction temperature in the range of up to about 80'C.
The resulting solution containing the copolymer is then optionally purif ied to remove unreacted monomer and other impurities. For example, the copolymer solution may be zo precipitated with a non-solvent, such as an ether compound, in particular diethyl ether, at a weight ratio of about l:l to l:lo, preferably about 1: 2 . The resulting precipitated copolymer is separated, and dried and then reconstituted in solution by adding additional solvent.
The copolymer containing solution may be combined with a conventional plasticizer such as polyethylene glycol (e.g. PEG-400), glycerine, mixtures thereof and the like to form a solution for impregnating the substrate.
The solution typically contains up to 40% by weight, preferably from about 2 to 20% by weight, of the hydrogel polymer. The hydrogel polymer may optionally contain up to about 60% by weight, preferably form about 15 to 60~ by weight of the plasticizer based on the weight of the plasticized hydrogel SU~STIT=E SHEET (RULE 26) S I
~ Wo 9S/26699 2 ~ ~6726 polymer. The balance of the solution is comprised of an organic solvent, typically from about 60 to 96% by weight of the solution .
The copolymer containing solution is applied to the wound-contacting substrate in any manner capable of uniformly impregnating the substrate. Dipping and spraying are two conventional methods for impregnating the solution although dipping is preferred. In this method, the wound-contacting substrate is dipped into a bath containing the solution. The impregnated substrate is then removed from the bath and allowed to dry. During the drying step, the solvent evaporates leaving the plasticized thermoplastic hydrogel on the substrate.
Alternatively, the hydrogel polymer, optionally with a plasticizer, may be melt processed through an extruder to impregnate the hydrogel polymer into the substrate. The hydrogel polymer in the form of a dry powder is placed into an extruder and heated. The melted hydrogel polymer is then formed into a sheet atop the substrate. The composite is then compressed until the hydrogel polymer impregnates the substrate.
The extent to which the hydrogel polymer is impregnated into the substrate is selected depending on the desired absorption capabilities of the wound dressing. Generally, the greater the amount of the hydrogel polymer impregnated, the greater the absorption capability of the wound dressing and the longer the wound dressing may be retained on the wound. The extent of impregnation is related to the dry weight of the applied hydrogel polymer per unit weight of the wound-contacting substrate. For most standard substrates, (e.g. cotton gauze) the dry weight of the impregnated polymer is in the range of from about 50 to 500%
by weight of the cotton gauze, preferably from about 60 to 150%
by weight.
The composite material of the present invention can absorb moisture up to about 15 times its weight, depending on the relative weight of the hydrogel polymer, without being dissolved away from the wound-contacting substrate. The hydrogel polymer SUBSTITUTE SHEET (RULE 26) .. ..... .. . .. .. . . . . . . . . . _ _ ~
'O:~Ql W095/26699 _ I~", 8 - 2 ~ 8 6 7 2 ~
is essentially in a dry state on the wound-contacting substrate and becomes slippery as it absorbs moisture. 51ippery or lubricous substrates serve the function of preventing adhesion of the substrate to the tissue of the wound. When the substrate is removed, the material comprising the substrate such as gauze is easil~ separated from the tissue without damaging the wound or inflicting paIn on the patient. The impregnation of a gauze like fibrous wound contacting substrate in accordance with the invention prevents shedding of lint and other particulate matter into the wound.
In accordance with another aspect of the claimed invention, the composite material containing the hydrogel polymer impregnated therein may have optionally thereon a material which improves handling or lubricity of the composite material. The preferred type of material for this purpose is a water-soluble biocompatible material in the form of fine particles (e.g. a powder). Such materials include gelatin, pectin, dextran and sodium carboxymethylcellulose. The amount of such materials should be sufficient to eliminate any residual tackiness o~ the composite material.
The composite material as described above may be incorporated into a variety of wound dressings including top dressings for superficial-type wounds as well as packing dressings for chronic and traumatic wounds. Examples of the former type of wound dressings are disclosed, for example, in U.S. Patent Nos. 3,425,412 and 4,513,739 and T).S. Patents disclosed therein, each of which is incorporated herein by reference. Common wound care products are also disclosed in Richard B. Ponder, et al. publication previously mentioned.
Composite materials in accordance with the present invention absorb significantly more exudate from a wound than conventional uncoated gauze-type materials. By way of example, if a conventional wound dressing required replacement 3 to 4 times over the course of an eight hour nurses shift, a wound dressing of the present invention may require only a single replacement.
SUBSTIT~JTE SHEET ~RULE 26) ~0 95/26699 T ~
21 86726 ~
67 ml of ethyl acetate was charged into a four-mouth round bottom flask. 32.175g of N,N-dimethylacrylamide and 0.825g of polystryene methacrylate macromonomer having a number average 5 molecular weight of 13, 000 (manufactured by Sartomer) were added to the flask. 0 . 033g of azobisisobutyronitrile dissolved in 2 . 0 ml of ethyl acetate was slowly added to the mixture under constant stirring until a completely clear mixture was obtained.
The flask was placed in an ethylene glycol bath maintained 10 at 50 C for 60 minutes. The bath temperature was gradually raised to 80-C over 15 minutes and the contents of the flask continuously mixed over the next 120 minutes. Thereafter, the reaction w~s terminated by removing the flask from the bath and allowing the reaction mixture to cool.
The resulting solution containing the graft copolymer composed of 2 . 5~6 by weight of polystyrene methacrylate was combined with 200 ml of diethyl ether, whereupon the graft copolymer precipitated. The supernatant liquid was decanted and the graft copolymer residue washed with diethyl ether until the 20 washings were completely clear.
The purified graft copolymer was combined with 300 ml of ethyl acetate and 27g of polyethylene glycol (PEG-400 Aldrich Chemicals) and stirred until a homogenous solution was obtained.
The solution was cast over folded silicone coated release papers 25 and allowed to dry overnight. The sheets were then placed in a vacuum oven and dried overnight at room temperature followed by drying at 50-C for at least 5 hours.
The copolymer sheet was immersed in water for 24 hours. The fully hydrated graft copolymer was removed from the liquid, 30 weighed, dried at So C for 24 hours and then reweighed. The equilibrium water concentration (EWC~ of the hydrated copolymer was 97~ as shown in ~able 1.
SUeSTlTUTE SHEET (RULE 26) WO 95/26699 ~CTIUS95/03813~
~ ~'t'~ ~ 10 ~ 2186726 EX~MPLE *AMOUNT OF MACROMONO~ER EWC (%) IN THE GRAFT COPOLY~ER
% BY ~EIGHT) 2.5 97 2 5.0 95 3 10.0 91 4 20. 0 75 5 30.0 63 1 - Percentage by weight of water absorbed based on the weight of 10 the hydrated sample, EXAMPT,~ 2-5 Example l was repeated for each of Examples 2-5 except that the amount of the polystyrene methacrylate macromonomer in the graft copolymer was increased to 5.~, lO.0, 20.0 and 30.096 by 15 weight, respectively. The results are shown in Table 1.
As shown in Table 1 each of Examples 1-5 show significant water absorption. It is further shown that the amount of water absorption increases as the amount of the polystyrene methacrylate macromonomer in the graft copolymer decreases.
2 O EXAMP~ ~ 6--J3 20. 0 parts by weight of the hydrogel polymer formed in accordance with the method of Example 3 was dissolved in 63 . 6 parts by weight of acetone containing 16 . 4 parts by weight of PE6-400 to obtain a clear hydrogel solution.
A woven type I gauze was dipped into the hydrogel solution for a few seconds. The residual solution was removed by passing the gauze through a pair of rollers. The gauze was heated in an oven at 120'C for three minutes to evaporate the solvent.
A 2" x 4" sample of the gauze (Example G) was placed on a piece of wet sponge in a chamber having a temperature Qf 40-C and a relative humidity o~ 75%. The weight of the sample was SUBSTITUTE SHEET (RULE 26) -WO 95/26699 r~
r ~ 1 8 6 7 2 6 ~, .
measured every 5 minutes during the first 30 minutes and every 30 minutes for the next two hours until saturation.
The amount of water absorbed by the sample was calculated as follows:
wate~ a~sorption _ wt(time) - wtl . .
at designated time ~ unit a~ea wt (time) = weight of the sample at the designated time wtl = dry weight of the sample before being placed on the sponge Two additional samples (Examples 7 and 8) were prepared and tested in the same manner as Example 6 except that the dipping 10 and drying process was repeated to increase the amount of the hydrogel polymer impregnated in the gauze material as indicated in Table 2.
WATER ABSORPTION
G/ ~z ~Y DROGEL
POLYMER AMOUNT
EXAMPLE ~EIGHT2 OF PEG3 5 MIN. 25 MIN.
15 6 30% 45% 61 63 753% 45% go 100 8639~ 45% 137 128 2 _ Based on the weight of the non-impregnated gauze.
3 - Based on the combined weight of the hydrogel polymer and PEG.
As shown in Table 2, Examples 6-8 provide significant water absorption in just 5 minutes and retain the absorbed water.
Table 2 further shows that increasing the weight of the hydrogel polymer increases the amount of water absorption of the gauze material .
SUBSTITUTE SHEET (RULE 26) r~
wo 9S/266gJ
- 12 - 2 ~ 8 67 2 6 EXAMpT.F g A sample of a hydrogel polymer impreynated qauze was prep2red in the same manner as Example 6. After drying of the hydrogel polymer, a small amount of sodium carboxymethyl-cellulose powder (6-30 mg/in2) was sprinkled onto both sides of the gau z e .
The thus treated sample was tested for water absorption in the same manner as Example 6. The test results showed that the sample (Example 5) exhibited a slight increase in the rate of water absorption over Examples 6-8. There was also observed a reduction in the adhesiveness of the surface of the gauze material .
t:~OMPARATI~'E EXAMPr,F:
The same type of gauze material employed in Examples 1-8 without tlle hydrogel polymer of the present invention was tested for water absorbency in the same manner as Examples 1-8. After 5 minutes, the amount of water absorbed was about 37 g/m2. After 25 minutes, the amount of water absorbed decreased to about 27 9/m2 ~
As shown in the Examples, the water absorbing capability of wound dressings impregranted with the hydrogel polymer in accordance with the present invention significantly exceeds the water absorbing capability of conventional gauze. In addition, the wound dressings of the present invention do not stick to the wound because, once exudate is absorbed, the wound dressing becomes slippery and does not adhere to tissue during the wound healing process.
SU9STITUTE SHEET ~RULE 26)
Claims (20)
1. A composite material for a wound dressing comprising:
(a) a fibrous wound-contacting substrate; and (b) a thermoplastic hydrogel forming polymer impregnated into said substrate.
(a) a fibrous wound-contacting substrate; and (b) a thermoplastic hydrogel forming polymer impregnated into said substrate.
2. The composite material of claim 1 wherein the thermoplastic hydrogel forming polymer is selected from the group A-B-A block copolymers, multiblock copolymers, graft copolymers zlnd polymer blends each incorporating a hydrophilic component and a hydrophobic component.
3. The composite material of claim 2 wherein the thermoplastic hydrogel forming polymer exhibits microphase separation having a hydrophilic/hydrophobic domain polymer system.
4. The composite material of claim 1 wherein the thermoplastic hydrogel forming polymer has an equilibrium water content in the range of from about 40 to 99%.
5. The composite material of slaim 2, wherein the A-B-A
type block copolymers have hydrophobic blocks selected from the group consisting of polystyrene, poly(methyl methacrylate), polyacrylonitrile, polyesters and polyamides, and the hydrophilic blocks are selected from the group consisting of polyethylene oxide, poly(hydroxyalkyl methacrylate) and derivatives thereof, polyacrylamide, poly(N-vinyl lactam) and polyacrylic acid.
type block copolymers have hydrophobic blocks selected from the group consisting of polystyrene, poly(methyl methacrylate), polyacrylonitrile, polyesters and polyamides, and the hydrophilic blocks are selected from the group consisting of polyethylene oxide, poly(hydroxyalkyl methacrylate) and derivatives thereof, polyacrylamide, poly(N-vinyl lactam) and polyacrylic acid.
6. The composite material of claim 2 wherein the multiblock copolymers are selected from the group consisting of copolymers of polyacrylanitrile and hydrophilic derivatives of acrylic acid and copolymers of polyethylene oxide and lactic acid.
7. The composite material of claim 2 wherein the graft copolymers are selected from the group consisting of poly(N,N-dimethylacrylamide-g-styrene) and poly(2,3-dihydroxypropyl methacrylate-g-styrene).
8. The composite material of claim 2 wherein the polymer blend is selected from the group consisting of a homopolymer or a copolymer of N-vinyl lactam and an acrylic copolymer containing a small proportion of acidic groups.
9. The composite material of claim 1 wherein the thermoplastic hydrogel forming polymer is present in an amount of from about 50 to 500% by weight based on the weight of the wound-contacting substrate.
10. The composite material of claim 7 wherein the thermoplastic hydrogel forming polymer is present in an amount of from about 60 to 150% by weight based on the weight of the wound-contacting substrate.
11. The composite material of claim 1 wherein the wound-contacting substrate is cotton gauze.
12. The composite material of claim 1 further comprising a water-soluble biocompatible fine particle material placed on the thermoplastic hydrogel forming polymer.
13. The composite material of claim 12 wherein the fine particle material is selected from the group consisting of gelatin, pectin, dextran and carboxymethylcellulose.
14. The composite material of claim 1 wherein the thermoplastic hydrogel film forming polymer contains up to about 60% by weight of a plasticizer.
15. A method of forming a composite material for a wound dressing comprising:
(a) forming a solution containing a thermoplastic hydrogel film forming polymer;
(b) applying the solution to a fibrous wound-contacting substrate; and (c) drying the solution on the fibrous wound-contacting substrate to said composite material.
(a) forming a solution containing a thermoplastic hydrogel film forming polymer;
(b) applying the solution to a fibrous wound-contacting substrate; and (c) drying the solution on the fibrous wound-contacting substrate to said composite material.
16. The method of claim 15 wherein the solution further comprises a solvent and a plasticizer.
17. The method of claim 16 wherein the solution contains up to 40% by weight of the thermoplastic hydrogel forming polymer.
18. The method of claim 15 wherein the amount of the plasticizer is up to 60% by weight of the total weight of the thermoplastic hydrogel polymer and the plasticizer.
19. A method of forming a composite material for a wound dressing comprising:
(a) melt processing the thermoplastic hydrogel polymer through an extruder;
(b) placing the extruded thermoplastic hydrogel polymer onto a substrate; and (c) applying pressure to the polymer and substrate to form the composite material.
(a) melt processing the thermoplastic hydrogel polymer through an extruder;
(b) placing the extruded thermoplastic hydrogel polymer onto a substrate; and (c) applying pressure to the polymer and substrate to form the composite material.
20. The method of claim 19 wherein the thermoplastic hydrogel polymer further comprises a plasticizer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/220,350 US5527271A (en) | 1994-03-30 | 1994-03-30 | Thermoplastic hydrogel impregnated composite material |
US08/220,350 | 1994-03-30 |
Publications (1)
Publication Number | Publication Date |
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CA2186726A1 true CA2186726A1 (en) | 1995-10-12 |
Family
ID=22823202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002186726A Abandoned CA2186726A1 (en) | 1994-03-30 | 1995-03-24 | Thermoplastic hydrogel impregnated composite material |
Country Status (8)
Country | Link |
---|---|
US (1) | US5527271A (en) |
EP (1) | EP0752840A4 (en) |
JP (1) | JPH09511168A (en) |
AU (1) | AU706203B2 (en) |
CA (1) | CA2186726A1 (en) |
NZ (1) | NZ283286A (en) |
WO (1) | WO1995026699A1 (en) |
ZA (1) | ZA952528B (en) |
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-
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-
1995
- 1995-03-24 NZ NZ283286A patent/NZ283286A/en not_active IP Right Cessation
- 1995-03-24 AU AU21299/95A patent/AU706203B2/en not_active Ceased
- 1995-03-24 WO PCT/US1995/003813 patent/WO1995026699A1/en not_active Application Discontinuation
- 1995-03-24 EP EP95914207A patent/EP0752840A4/en not_active Withdrawn
- 1995-03-24 CA CA002186726A patent/CA2186726A1/en not_active Abandoned
- 1995-03-24 JP JP7525795A patent/JPH09511168A/en active Pending
- 1995-03-28 ZA ZA952528A patent/ZA952528B/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP0752840A4 (en) | 1997-07-02 |
JPH09511168A (en) | 1997-11-11 |
US5527271A (en) | 1996-06-18 |
AU2129995A (en) | 1995-10-23 |
NZ283286A (en) | 1998-08-26 |
AU706203B2 (en) | 1999-06-10 |
EP0752840A1 (en) | 1997-01-15 |
ZA952528B (en) | 1996-09-30 |
WO1995026699A1 (en) | 1995-10-12 |
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