Pressure-sensitive adhesive film article having high moisture vapor transmission

41028 CAN 8A --1-- ' 133~3 PRESSURE-SENSITIVE ADHESIVE FILM ARTICLE HAVING HIGH MOISTURE VAPOR TRANSMISSION S ':

Field of the Invention , This invention relates to a pressure-sensitive adhesive film article.

In particular, this invention relates to an article comprising a film of 10 pressure-sensitive adhesive~ which article is useful in the moist healing of wounds.

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Background of the Invention ` - ~ -.

In recent years, the technique of wound repair 15 known as moist healing has become well established. It is an improvement in many cases over the traditional method of letting a wound dry out, forming a scab or crust over the surface, followed by regrowth of tissue underneath the scab. It has been found that, relative to dry healing, 20 moist healing often results in cleaner repair, with less scarring and less pain to the patient than dry healing, especially when the wound is an extensive burn or large abrasion. Dressings for moist healing therapy are frequently made of thin films of synthetic polymers such as 25 polyurethanes as described in U.S.

Patent No. 3,645,835.

One of the characteristics of these films is their. ability to selectively allow water molecules ("moisture vapor") to pass through them while preventing the passage of liquid water or aqueous solutions and, most importantly, bacteria.

30 By careful selection of film and adhesive, a dressing can be provided which keeps a wound moist and sterile, but which allows excess liquid to evaporate. It also conforms well to the skin, and is unobtrusive in use.

Such dressings, however, have several 35 disadvantages when used with certain kinds of wounds. When a wound is seeping copiously, the "moisture vapor transmission" (MVT) capability of the film cannot remove ~ ~3~0~9~ --2-excess liquid fast enough. As a result, fluid may accumulate under the dressing which can result in skin maceration.

In practice, a film of sufficiently high MVT ~ to be useful as a dressing on highly exudative wounds would 5 have to be too thin to be practical. Even film dressings in commercial use today are so thin and flimsy that they are extremely dif~icult to apply without special delivery means such as those described in U.S.

Patents 4,513,739, 4,598,004 and Canadian Patent No. 1,192,825.

The problem of ha~dling copiously-seeping wounds was addressed in U.S.

Patent 4,499,896 by providing a reservoir dressing with one or more extra layers of thin film, sealed together at their peripheries, ~o form pouches into which excess liquid can flow temporarily. These 15 pouches or reservoirs have additional surface area through which moisture evaporation can take place. These dressings have found utility, but are clearly more complicate~ and costly than dressings made from a single film.

Another disadvantage of conventional thin film 20 dressings is that they provide very little mechanical cushioning to a wound. Wound protection against bumps and scrapes is not addressed by these thin dressings.

Foam backings for wound dressings are known (e.g.

MicrofoamTM brand surgical tape, 3M Co.) where the 2S foam provides a thicker, more conformable, more cushioning material than would be provided by the same weight of unfoamed backing. The backing of MicrofoamTM brand surgical tape is open cell polyvinylchloride which is not a barrier for micro organisims. If the polyvinylchloride was 30 made with closed cells, it would not have a sufficiently high MVT for moist wound healing without skin maceration.

U.S.

Patent No. 4,559,938 (Metcalfe) discloses an adhesive dressing comprised of a backing and a conventional pressure-sensitive adhesive. The backing is a film formed 35 from a blend of a continuous matrix of 1,2-polybutadiene and an incompatible polymer which forms a discrete particulate phase within the matrix. This film is .~,, ~, . ~' . ' ' ; , ~ 3 3 ~ ~ 0 3 --3-stretched to introduce a plurality of small, preferably closed, voids in the film which nominally enhance the moisture vapor permeability of the film. It is believed that the moisture vapor permeability of the dressing 5 (through film and adhesive) is too low to be used in moist wound healing without skin maceration.

Thus, there exists a need for a wound dressing which provides controlled transmission and/or absorption of water vapor away from a wound so that the wound remains ~10 moist but not excessively s~, and which is also thick and flexible enough to alleviate the need for elaborate delivery means and to provide mechanical cushioning of a wound. ` 15 Summary of the Invention According to the present invention, there is provided a pressure-sensitive adhesive article for~use on skin comprising a continuous film of pressure-sensitive adhesive having dispersed therein a discontinuous gaseous 20 phase contained within voids within said film, which gaseous phase constitutes at least 10 percent of the volume of said pressure-sensitive adhesive. The film has a moisture vapor transmission and absorbency sufficient to permit moist healing of wounded skin without skin 25 maceration, e.g., an MVT of at least about 400 g/m2 per 24 hours measured at 40C and 80% relative humidity .

differential.

The adhesive film of the invention has cellular voids containing a gaseous phase to effect control of 30 adhesive thickness and to provide a multiplicity of microreservoirs or micropouches. The film allows water vapor to pass at a controlled rate by diffusion of water vapor through the adhesive surrounding the voids and collection of water vapor in the voids, but prevents liquid 35 media (e.g., water) and bacteria from traversing the film.

This controlled diffusion of water vapor allows for the presence of an optimal amount of moisture at the site of a '" ......... ~ :

.,., :,' ' . .

' '`` 1 3 3 ~ ~ 0 ~ -4healing wound covered by the film. The cellular construction of the film also provides mechanical cushioning of the wound.

In a preferred embodiment of the adhesive article 5 of the invention, a film of cellular pressure-sensitive adhesive is in contact with one face of a conformable sheet.

The conformable sheet preferably has high moisture vapor transmission i.e., at least about 1000 g/m2 per 24 hrs at 40C and 80% humidity differential.

Another aspect of/this invention relates to a method of preparing a pressure-sensitive adhesive article as described above comprising~ a) forming a hydrophilic polymerizab~è composition which polymerizes to a pressure-sensitive adhesive state;

b) foaming said composition;

c) coating a carrier with said foamed composition;

and d) polymerizing said coating to a pressure-sensitive adhesive state.

The hydrophilicity of the polymerizable composition may be provided by the inclusion of: (1) a hydrophilic, ethylenically unsaturated monomer, e.g., acrylic acid or an acrylate or acrylamide terminated polyether; (2) by a ~ 25 hydrophilic additive, e.g., a polyhydric polyol, or polyether; or (3) both a hydrophilic monomer and a hydrophilic additive. The degree of hydrophilicity required of the polymerizable composition is that degree which is sufficient to provide a pressure-sensitive 30 adhesive having the desired degree of moisture vapor transmission.

Detailed Description The pressure-sensitive adhesive films of this 35 invention must have a sufficiently high moisture vapor transmission and absorbency to permit moist healing of a wound without skin maceration. Moist healing is the 1 3 ~ 3 --5-retention at a wound of an optimum amount of moisture which (1) prevents the formation of a scab, (2) increases the rate of epithelial cell migration, and (3) does not allow pooling of moisture or wound exudate. Skin maceratior. is a 5 deleterious effect of pooling of excess liquid, e.g., water or bodily fluid, on the normal skin surrounding a wound.

Skin maceration is indicated by whitening and softening of the affected skin. In general, adhesive films of this invention having a moisture vapor transmission of at least lO about 400 g/m2 per 24 hrs measured at 40C and 80~ relative humidity differential are sufficiently absorptive and transmissive to avoid skin maceration and promote moist wound healing. The moisture vapor transmission is preferably at least about 500 g/m2 per 24 hrs., and most 15 preferably from about 600 to about 2400 g/m2 per 24 hrs.

The adhesive film useful in this invention is cellular, i.e., non-porcus, such that it possesses substantially total impermeability to liquid water and bacteria.

Moisture vapor transmission as referred to herein 20 and in the claims, except as otherwise noted, refers to moisture vapor permeability determined in accordance with the test described below.

Impermeable to liquid water as used herein means impermeable to liquid water as indicated by the dye penetration test described below~ The adhesive film is rendered moisture vapor permeable and absorbent by the hydrophilicity of the adhesive composition and the cellular voids in the film.

The thickness of the adhesive film, along with the hydrophilicity and the voids, affects the absorption 30 capacity of the adhesive film. The adhesive film is rendered hydrophilic by the addition of hydrophilizing agents to the polymerizable premix from which the adhesive is prepared such as those described below.

As used herein, "percent void volume" means that 35 portion of the thickness of the cellular adhesive membrane attributable to cellular voids. Percent void volume is conveniently measured by the equation:

~` 1 3 3 ~ --6-dU-df ' ' ~V = ~ x 100 wherein du is the unfoamed density and df is the foamed density of the adhesive. Unfoamed density can be 5 determined from the density of the starting materials or by compressing the foamed adhesive. Adhesive films according to the invention should have void volumes of from about 10 to about 85 percent. The higher the void volume of the adhesive film, the greater the MVT, absorbency, 10 conformability, and cushioning ability of the dressing. The adhesive films of this invention possess useful absorbency in addition to their ability to transmit water vapor. ~hen the film is composed of an adhesive having low absorbency, the difference in absorbency between 15 the foamed state and the unfoamed is pronounced (See Examples 1-6). This effect is less pronounced in the case of adhesives which are already highly absorbent, but in both cases the end product has the ability to absorb significant quantities of water. The water is not easily 20 removable from the foam by squeezing. This is a useful distinction from conventional reservoir dressings used on highly exudative wounds, wherein the contents of the reservoirs may leak out when the dressing is manipulated.

Also, typical pressure-sensitive adhesive films 25 of the invention have remarkably good flexibility and conformability which are advantageous properties in a wound dressing.

The pressure-sensitive adhesive films of the invention are derived from a hydrophilic polymerizable 30 premix into which cellular voids are introduced. The premix is made hydrophilic by the addition of a hydrophilizing agent such as a hydrophilic, ethylenically unsaturated monomer, a hydrophilic additive or both.

Preferred hydrophilic additives are polyhydric alcohols, 35 polyethers, or mixtures thereof. The polyhydric alcohol or polyether is present in the premix in an amount sufficient to raise the moisture vapor transmission of the adhesive to the desired level. This amount ranges, in general, from ~.L 13~0~ :

about 20 to about 85 parts by weight of the premix, with about 30 to about 70 being preferred. Examples of useful polyhydric alcohols and polyethers include glycerin, propylene glycol, polypropylene oxide glycols, polyethylene 5 oxide glycols, 1,2,4-butanetriol, and sorbitol and mixtures thereof. The dihydric alcohol, ethylene glycol is useful in the present invention, but may cause dermal reactions which limit its utility. ~ The hydrophilizing agent may also have ethylenic 10 unsaturation which will all~w it to copolymerize with other free radically polymerizable materials in the premix as described belo~. For example, a polyether polyol can be terminated with acrylic or methacrylic acid; or a reactive derivative thereof, to yield an acrylate or methacrylate 15 terminated polyether, e.g., poly(oxyethylene)acrylate.

Also, an amine terminated polyether can be terminated with acrylic or methacrylic acid, or a reactive derivati~ve thereof, to yield an acrylamide or methacrylamide terminated polyether, e.g, N-poly(oxypropylene)acrylamide.

The premix is also comprised of an unsaturated free radically polymerizable material which when polymerized renders the premix pressure-sensitive adhesive, and which is preferably miscible with the hydrophilizing agent.

This material may consist of a single monomer or a 25 mixture of comonomers. These monomers or comonomers are present in the premix in amounts o from about 10~ to about 10 parts by weight of the premix preferably from about 50 to about 20. Examples of useful monomers or comonomers are alkyl acrylates having an average of 4-12 carbon atoms in 30 their alkyl groups, acrylic acid, methacrylic acid, and salts thereof, acrylamide, methacrylamide, hydroxyalkylacrylates, hydroxyalkylmethacrylates, acrylonitrile, methacrylonitrile, cyanoethylacrylate, maleic anhydride and N-vinyl pyrrolidone.

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-8It is preferred that the premix contain a plasticizing component which is conveniently provided by the polyether or polyol hydrophilic additive or the polyether- or polyol-containing monomer.

The premix is also preferably comprised of a thickening agent of polymeric material which is preferably soluble in the polymerizable composition.

These polymeric materials are present in the premix in amounts of about 0.1 to about 70 parts by weight of the premix.

Examples of 10 useful poly~eric materials are sodium carboxymethyl cellulose, hydroxyethylcellu~ose, methoxyethyl cellulose, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyvinylethers, copolymc~s of maleic anhydride and polyvinylethers, starch, hydroxypropyl15 cellulose, polyacrylamide, copolymers of alkyl acrylates and acrylic acid or its salts, polyethylenimine, ethylene oxide polymers and propylene oxide polymers.

The adhesive film is preferably crosslinked. One means of crosslinking is the inclusion of a multi20 ethylenically unsaturated, free radically polymerizablematerial, generally in an amount of from about 0.1 to about 5 parts by weight per 100 parts of the polymerizable materials in the premix. Examples are triethylene glycolbis-acrylate, triethylene glycol bis-methacrylate, ethylene -~ 25 glycol-bis-acrylate, ethylene, glycol-bis-methacrylate, and methylene-bis~acrylamide. These multi-ethylenically unsaturated, free radically polymerizable materials crosslink the polymeric material. Other means of crossiinking include crosslinking the polymer with 30 radiation, e.g., E-beam.

Polymerization of the premix is carried out using conventional methods, e.g. ultra-violet radiation, heat, E-beam and the like. Polymerization by ultra-violet radiation or heat is facilitated by the presence of a free 35 radical initiator which is soluble in the polymerizable ~ composition. The initiator is generally present in an amount of at least about 0.01 parts by weight per 100 parts l33a~ --9- of the polymerizable materials in the premix. Examples of useful thermal initiators are benzoyl peroxide, azobisisobutyronitrile, di-t-butyl peroxide, and cumyl peroxide. Examples of useful photoinitiators are 5 disclosed in the article "Photoinitiators - An Overview" by G.

Berner et al in the Journal of Radiation Curing (April, 1979) pp. 2 through 9. The preferred photoinitiator is benzildimethylketal.

It is often desirable to include a 10 surfactant in the premix, preferably a silicone or fluorochemical surfactant. By doing so, the stability and density of the frothed premix are improved. These surfactants are not always necessary, but when used, are present, as shown in Table III, below, in amounts 15 ranging from 0.5 to 6 parts by weight of the premix.

Examples of useful surfactants are described in U.S.

Patent No. 4,415,615. A preferred fluorocarbon surfactant is available under the trade name FC 430, from the 3M Company.

Filler materials can also be incorporated in the premix prior to frothing and coating of the premix or during coating of the premix, the amount of filler being dependent upon the type of filler material being used and the properties desired~ Useful filler 25 materials include fibrous reinforcing strands, woven and non-woven reinforcing fabrics, glass beads, plastic hollow microspheres or beads, viscosity-adjusting agents, pigments and absorbent particles. These may be used to enhance the internal strength of the adhesive 30 film or to modify the adhesive and absorbent properties as shown in Example 22, below.

The pressure-sensitive adhesive films of the invention may be prepared by the methods disclosed in U.S.

Patent No. 4,415,615. In general, the process 35 involves the polymerization of a premix containing voids to a pressure-sensitive adhesive state by conventional means. The cellular voids area preferably ,.. .. ., . ... ,~ ,, t ~ - r i ~ ~ ,, ' . ~ ., 4.; ~ ~L33~03 ~ --10-formed in the premix before coating the premix onto a carrier.

The premix can be coated by any suitable means, which will not destroy the cellular voids in the foamed premix.

Absorption capacity, conformability, MVT and cushioning may be controlled by varying the thickness of the adhesive film.

Thickness of the adhesive film is determined by the dimensions of the aperture through which the frothed premix passes as it is being coated onto a lO carrier. Adhesive films having a thickness ranging from about 0.07 to about 1.7 mm a~e generally suitable. The minimum thickness of the adhesive film is dependent upon the maximum cell size generated in a particular film which is, in turn, determined by the processing conditions and 15 chemical properties of the premix. For example, a surfactant-containing premix would result in an adhesive film with smaller cell diameters and could be coated thinner without the risk of discontinuities than a premix which does not contain surfactant. The maximum thickness 20 is limited by the MVT desired and, as a practical matter, the amount of energy available to effect a complete cure.

An adhesive film of the present invention is preferably made by the sequential steps of:

(1) foaming a premix, (2) coating the foamed premix onto a carrier, and (3) polymerizing the coated premix in situ to a pressure-sensitive adhesive state.

Foaming of the premix is conveniently accomplished by whipping a gas, e.g. air, into the premix as disclosed in 30 U.S.

Patent No. 4,415,615. Foaming of the premix could also be accomplished by including a blowing agent in the premix which can be volatilized to produce cellular voids in the adhesive.

Because the viscosity of a mixture of 35 polymerizable monomers tends to be too low to provide a ~ - coatable froth or foam, several techniques have been used to thicken the mixtures before frothing or foaming, to ~ 3 ~ 3 --11- provide a composition having a viscosity in the range of 1000 to 40,000 cps. One method is to add thickeners such as those described above to the polymerizable premix.

Another method is to thicken the premix with a partially S photopolymerized solution or syrup of isooctylacrylate (IOA) and acrylic acid (AA), or IOA and AA in polypropylene :

glycol.

After coating the foamed composition onto a substrate, the polymerization can be initiated by 10 ultraviolet radiation as taught in U.S.

Pat.

No. 4,181,752.

In situ polymerization can also be effected by electron beam. Because air tends to quench photopolymerization, the foaming gas is preferably inert, such as nitrogen or carbon dioxide.

When the polymerization is to be effected by ultraviolet radiation, the polymerizable coating is preferably protected from air by polymerization in~an inert atmosphere or by the use of a plastic film overlay which is fairly transparent to ultraviolet radiation and has a 20 low-adhesion surface. Biaxially-oriented polyethylene terephthalate film which is about 75% transparent to ultraviolet radiation is very useful as an overlay. If the underlying carrier also has a low-adhesion surface, both the carrier and the overlay can be stripped away so that :

25 the self-supporting adhesive film may be obtained.

Normally, one does not wish to have an .

unprotected film of the adhesive at this point in production. In practice, one may either retain the original carrier and overlay or replace one or both (e.g., 30 by lamination) with a liner or backing more suitable for the product. For example, one may wish to use a release liner or a backing bearing a logo, a decorative design, or instructions for use of the product. Ideally, the carrier and the plastic film overlay have sufficiently attractive 35 appearance and properties of low adhesion to the adhesive '~"'< ,~ f ~ 3393~ -12film that they can be used as protective liners for each face of the adhesive through converting operations and, most preferably, until the final product reaches the hands of the user. For example, when the pressure-sensitive 5 adhesive film is to be used as a means of attaching an ostomy appliance to the skin of a patient, it is desirable to have easy-release liners on each face which are removed sequentially. For example, one might attach the first face of the adhesive to the skin and then an appliance to the 10 second, exposed face of the. adhesive.

When the adhesive film is used without a backing, it may be desirable to embed a layer of reinforcing material in the film to structurally suppo~t the film.

This can be accomplished by coating a carrier with a layer 15 of the polymerizable premix, laying down a layer of reinforcing material, e.g. a fabric, on the coating of premix and coating the exposed layer of reinforcing materials with another portion of polymerizable material.

It may be necessary to polymerize the first coating of 20 polymerizable premix before laying down and coating the layer of reinforcing material if the energy used to initiate polymerization radiates from a single source which is not sufficient to completely polymerize the premix throughout its entire thickness.

- 25 When making a wound dressing, one face (the skin-contacting side) of the adhesive film is cov.ered with an easy-release liner, which is removed immediately prior ~ ~ to use, but the other face is usually covered with a ~ ~ backing, i.e., a material which reduces or eliminates the ;;

tack of that face of the adhesive and which is permanently attached to the adhesive layer.

The backing must not reduce the MVT of the dressing below the required level. A number of materials are suitable for this purpose.

For example, a coating of a finely divided inert solid, e.g., 35 talc, or a microporous non-woven fabric or plastic film, e.g., polyethylene, polyvinylchloride, etc. can be used. A very thin continuous film (e.g., ca 25 micrometers) of ~33~03 -13polyurethane, e.g., EstaneTM available from ~. F.

Goodrich, is preferred as a backing. This polyurethane is a polyoxyethylene polyurethane which contributes to the high MVT.

This film has several advantages. It is very soft, 5 and conforms well to body contours. It possesses high moisture vapor transmission (ca 1500 gm/m2/hr), allowing absorbed water vapor to escape from the adhesive into the atmosphere. It is also impervious to bacteria.

For use, a dressing of this invention is attached lO to a patient's skin over a wound. In the normal healing process, aqueous fluid-bearing cells, etc. needed for wound repair, will ooze from the damaged tissue. When the wound is of considerable size, excess fluid may be`produced. As a result of f~uid production a significant pressure will 15 build up in the wound cavity. As described above, the adhesive film already possesses a significant moisture vapor transmission (MVT), so that water vapor from~the wound exudate will begin to penetrate the film. As it penetrates, it can encounter one or more of the small voids 20 or reservoirs in the adhesive film. The effective thickness of the dressing as seen by molecules of water vapor passing through the dressing, is controlled by the number of reservoirs the molecules encounter, and by the thickness of the solid zones traversed by the molecules.

25 It will be appreciated that the absorption capacity of the film is dependent upon both the diffusion of water molecules into the solid zones, and the capacity of the reservoirs to contain liquid water which has diffused into ~them as vapor A film with only a relatively small number 30 of reservoirs and relatively large solid zones between reservoirs would have a lower MVT than a low density, closed-cell f~am adhesive film, in which the solid zones between the reservoirs are very small. A dressing of the latter type will have very high MVT relative to 35 conventional dressings of comparable thickness. As a result, dressings of the present invention can provide ~ 330~03 -14optimum MVT previously obtainable only with films that are too thin and flimsy to handle easily.

There may be occasions when it would be desirable to include an extra, protective backing or embedded 5 reinforcing layer, e.g., a fibrous and/or fabric filler as discussed above, when, for example, a dressing may be expected to be subjected to mechanical wear-and-tear. Such a backing or reinforcing layer need not be functional from the standpoint of controlling MVT, so long as it doesn't 10 reduce the MVT of the dressdn~ below the desired level.

However, backing and reinforcing layers which affect MVT may be utilized to achieve the MVT properties desired in the dressing. ~ ~ Examples ~ ;

General Procedure For Frothing And Coating Adhesives The uncured adhesive and surfactant solutions were pumped s;multaneously using two Zenith QM1416 metering systems, one system at a 20:1 ratio and the other at a 30:1 20 ratio, (Fenner DC Controllers) and two Zenith gear pumps (3MC 5334 and BPB 5566) through a 99 mm single-stage mixer (SKG Industries) with introduction of nitrogen gas. The resulting frothed premix was coated between two lowadhesion carriers, at least one of which was transparent to 25 UV radiation. The thickness of the coating was controlled by a nip roll or knife.

The coating was irradiated through the transparent film(s) with 15 watt fluorescent black lights having a maximum at 350 nm. Conditions for frothing and coating were as follows unless otherwise noted.

Uncured adhesive flow rate 96 cc/min.

Surfactant flow rate 4 cc/min.

N2 flow rate 100 cc/min.

Mixer Speed 300 rpm Back Pressure 211 g/cm2 Adhesive Thickness 0.760 mm Exposure 4 x 106 ergs ,t,., , :,' ~ ' . ,, ' ' ;. ,' ' ,. '. ' . , ` , ' ' : ' -' ~33~03 -15Following the curing process, one of the low-adhesion carriers was removed and the adhesive was laminated onto a 0.025 mm thick, a polyoxyethylene polyurethane film backing prepared as follows. A one mil, i.e., 25 micron film of 5 EstaneTM 58309-021 polyurethane resin (B.F.

Goodrich, Cleveland, Ohio) was extruded using a three-quarter inch ~1.9 cm) Rheomex Model 252 screw extruder (manufactured by Haake, Saddlebrook, New Jersey), a sheeting die and a melt temperature of 190C. The film was extruded onto the back 10 side of a clay-coated side of~a 78 pound (35412 grams) paper (releasable layer) which was clay-coated on one side by roll coating (No. 70-05-04-000, Boise Cascade Corporation, International Falls, Minnesota~; Immediately after extrusion the paper/resin combination was passed 15 through a nip roll at 80 psi (5624 grams per square centimeter).

Premix Starting Materials The following materials were used to prepare the 20 adhesives shown in the following examples.

Thickeners Thickener A. A solution composed of 30 parts of isooctylacrylate, 30 parts of acrylic acid, 40 parts of ;

25. polypropylene gl~col-425 (PPG-425, Dow Chemical), and 0.04 parts "Irgacure"~r651 (2,2-dimethoxy-2-phenylacetophenone, Ciba Geigy) was simultaneously purged with nitrogen gas and irradiated with fluorescent black lights until a temperature of 79C was attained. The exposure was then 30 stopped and tha reaction was quenched with air. The resulting syrup had a viscosity of 11,000 cps at 25C and contained 75% residual acrylate monomer.

Thickener B. A solution containing 25 parts of isooctylacrylate, 25 parts of acrylic acid, 50 parts of 35 polypropylene glycol 425 and 0.04 parts of "Irgacure" 651 ~''' was simultaneously purged with nitrogen gas and irradiated with fluorescent black lights until a temperature of 77C 133~3 -16was attained.

The irradiation was then stopped and the reaction was quenched with air.

The resulting syrup had a viscosity of 6200 cps at 25C and contained 71% residual acrylate monomer.

Thickener C. A solution containing 80 parts of isooctylacrylate, 20 parts of acrylic acid and 0.04 parts of "Irgacure" 651 was purged with nitrogen and irradiated with fluorescent black lights.

The resulting syrup had a viscosity of 11,000 cps at 25C and contained 89% residual 10 monomer. ~;

Thickener D. A solution containing 60 parts of glycerin and 40 parts of "Goodrite'~K722 (a 37% aqueous solution of polyacrylic acid, MW 100,000, B:F.

Goodrich) ~-~ (PAA) was fed through a film extruder available from LUWA 15 Co. at a rate of lOOlbs./hr., 160F and 5 mm Hg. The resulting syrup, consisting of 7g.8% glycerin, 19.2% polyacrylic acid and 1.0% H2O, had a viscosity of ~00,000 cps at 25C.

Thickener E. A solution containing 90 parts of 20 isooctylacrylate, 10 parts of acrylic acid and 0.04 parts of "Irgacure" 651 was purged and irradiated as in C, above.

The resulting syrup had a viscosity of 4330 cps at 25C.

Thickener F.

Sodium carboxymethyl cellulose, Type 7H, Hercules, Inc.

Thickener G.

Polyvinylpyrrolidone K-90, GAF.

Thickener H.

Low viscosity chitosan from Pro1an Laboratories, Inc.

Thickener I. A solution containing 80 parts of isooctylacrylate, 20 parts of acrylic acid and 0.04 parts 30 of "Irgacure" 651 was simultaneously purged with nitrogen gas and irradiated with fluorescent black lights until a temperature of 67C was attained. The irradiation was then stopped and the reaction was quenched with air. The resulting syrup had a viscosity of 32,000 cps at 25C.

.

R ~ D~ I~q ~R ~ ~ 3 ~ 3 -17 Photoinitiators Photoinitiator A: 2,2-dimethoxy-2-phenylacetophenone available as "Irgacure" 651 from Ciba-Geigy.

Photoinitiator B: hydroxycyclohexyl phenyl ketone available 5 as "Irgacure" 184 from Ciba-Geigy.

,~ Difunctional Monomers TGBM: Triethylene glycol bis-methacrylate available , from Sartomer Company.

- 10 EGBM: Ethylene glycol,~bis-methacrylate available from Sartomer Company.

Surfactants `` Surfactant A. A solution of 70 parts of polypropylene 15 glycol having a molecular weight of 425, 40 parts of a fluorosurfactant available as FluoradTM FC171 from 3M ,~ and 60 parts of a fluorosurfactant available as Fluorad FC431 from 3M. ,"~ Surfactant B. A solution of 50 parts of polypropylene 20 glycol 425 and 100 parts of a fluorosurfactant available as FluoradTM FC431 from 3M.

Surfactan~ C. A solution of 50 parts of polypropylene glycol 425 and 50 parts of a fluorosurfactant available as FluoradTM FC430 from 3M.

25 Surfactant D. A solution of 50 parts of polypropylene glycol-425 and 50 parts of a fluorosurfactant available as FluoradTM FC171 from 3M.

Surfactant E. To a solution of 60 parts of a fluorosurfactant available as FluoradTM FC431 from 3M and 30 40 parts of a fluorosurfactant available as FluoradTM FC171 from 3M was added 30 parts of carbitol acetate. under reduced pressure, 30 parts of ethyl acetate were removed by distillation.

Test Methods The tests used to evaluate the samples and generate the results shown in Table 4 were accomplished as follows.

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` ~-^` 1 3 ~ 3 -18Moisture Vapor Permeability A modified Payne cup method is used.

The method ~ comprises the following steps: ~(1) A 1-3/8 inch (35 mmm) diameter sample of material to be tested containing no perforations is cut.

(2) The sample is entered between the adhesive surfaces of two foil adhesive rings, each having a one inch (2.54 cm) diameter hole.

The holes of each ring are carefully aligned.

Finger presure ','-~ isused to form a,oil/sample/foil assembly that is flat, wrinkle-ftee and hs no void areas in the exposed sample.

(3) A 4 ounce glass jar is filled half`full of distilled water.

The jar is fitted with a screw on cap having a 1.50 inch diameter hole in the center thereof and with a 1.75 inch diameter , rubber washer having a 1.12 inch diameter hole in its center. ~;

(4) The rubber washer is placed on the lip of the jar and the foil/sample assembly is placed on the rubber washer.

The lid is then screwed loosely on the jar. ~ , (5) The assembly is placed in a chamber at 100F (38C) and 20 percent relative humidity for four hours. ~ ,(6) The cap is tightened inside the chamber so the sam~le material is level with the cap (no bulding) and the rubber washer is in proper seating position.

(7) The assembly is removed from the chamber and weighed immediately to the nearest 0.01 gram (initial weight -Wl).

(8) The assembly is returned to the chamber for at least 18 additional hours. ' ' (9) The assembly is removed from the chamber and weighed immediately to the nearest 0.01 gram (final weight -W2 ) . ..

133~03 --19- (10) The water vapor transmission in grams of water vapor transmitted per square meter of sample area in 24 hours is calculated according to the following formula:

MVT = (W1 - W2) 4.74 x 104 T (hours) W1 = initial weight (grams) W2 = final weight (grams) T = time (hours) When a 1/2 inch sample is tested, the formula is -~ changed to the following~ r~ MVT = (W1 - W2) 1.9 x 105 T (hours) (11) Three samples of each material should be run and the average taken.

Absorbency To determine absorbency, a sample of the cured ~ - 20 adhesive was initially weighed and then immersed in deionized water at room temperature for one hour. The sample was then retrieved and weighed again .

Absorbency ~is reported as the difference in weight divided by the initial weight. optimal absorbency varies greatly 25 depending upon the intended use of the adhesive film. For use on intact skin, low absorbencies are acceptable.

Highly exudative wounds require higher absorbency films.

Absorption capacity of the film can be controlled by the thickness of the film. In general, an absorbency of at 30 least 50% over 1 hour is preferred.

180 Peel Adhesion One inch (2.54 cm) wide test samples of the cured adhesive are self-adhered to the skin of a human volunteer ~ 35 under the weight of a 2.04-kg hard rubber roller, 2 passes ; in each direction.

After 15 minutes dwell, 180 peel is .

-" 13~0~ :

-20measured by moving the free end of each tape away from the skin at a rate of about 0.5 cm per second (using a tensile tester). Samples were tested immediately after application (Initial) and at 6 hours after application (Final) and 5 results reported. Preferred adhesives have an initial adhesion of at least about 5 g/cm, more preferably at least ~ 10 g/cm and most preferably at least about 20 g/cm. The final adhesion is preferably less than double the initial adhesion.

1 0 ' ' Density The density of the samples was measured by simply weighing a sheet of each sample and measuri~g the area and depth of the sheet to calculate volume. ~ ` Examples 1-5 and Comparative Example A Examples 1-5 and Comparative Example A, 20 summarized in Table I, below, were prepared by combining the thickener specified with additional isooctylacrylate ("IOA") and acrylic acid monomers ("AA") and polypropylene glycol ("PPG") to give the IOA:AA:PPG ratios (ratio includes copolymerized IOA and AA in thickener) and % 25 solids ( IOA-AA copolymer) indicated in Table I.

"Irgacure" 651 was added at a level of 0.1% by weight.

Triethylene glycol bis-methacrylate (TGBM) was added at the levels indicated and the mixture was mechanically stirred.

The resulting solution was frothed in a 96:4 ratio with 30 surfactant E, coated and cured as described in the "General Procedure".

:~:

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-21 TABLe I Composition of Examples 1-5 and Comparative Example A .: :

MonomerSolventThickener Solids TGBM Example Ratio (wt. %) twt- %) (wt. %) Thickness (mm) 1 IOA-AA-PPG A (69-3) 10.4 2.9 0.76 22.5-22.5-55 10 2 IOA-AA-PPG A (6~.3) 10.4 2.9 0.25 :

22.5-22.5-55 ' 3 IOA-AA-PPG C (50) 7.3 1.5 0.76 40-20-40 '` 4 IOA-M-PPG C (44) 6.4 2.0 0.76 35-25-40 IOA-M-PPG C (50) 7.3 2.0 0.76 40-20-40 ~ ;

A IOA-AA E (100) --- --- 0.76 90-10 Examples 6-18 Examples 6-18 were prepared by combining thickener D [an 80/20 glycerin-polyacrylic acid ("PAA") solution] with acrylic acid and glycerin to give the :

25.AA:glycerin:PAA ratio indicated in Table II.

To this was :~ added "Irgacure" 651 at a level of 0.1~, difunctional ~.:.. monomer TGBM or EGBM, and, optionally, lithium hydroxide as indicated and the mixture was mechanically stirred. The resulting solution was frothed in combination with the 30 surfactant indicated, coated and cured according to the "General Procedure". .~ -`- `~:

~ 3 ~ 3 ~ :

-22TABLe II : osition of Examples 6-18 Difunctional Ex. AA Glycerin PAA Monomer LiOH Surfactant Thickness 5 No. (wt. %) (wt. 7o') (wt. X? (wt. % ) (wt. 7~) (wt. ~) (mm) 6 25 67.5 7.5 TGBMt0.2) ~~ E(4) .762 7 25 67.5 7.5 TGBM(0.2) -- E(4) .330 8 25 67.5 7.5 TGBM(0.2) ~~ E(4) .127 9 30 60 10 TGBM(0.3) ~~ E(4) .762 10 10 25 67.5 7.5 T~BM~0.2) -- C(4) .762 11 ~5 67.5 7.5 TG~h(0.2) ~~ C(2) .762 12 25 67.5 7.5 TGBM(0.2) ~~ C(l) .762 13 25 67.5 7.5 TGBM(0.2) -- '` none .762 14 25 67.5 7.5 TGBM(0.2) ~~ D(4) .762 15 25 67.5 7.5 TGBM(0.2) ~~ A(4) .762 16 25 67.5 7.5 TGBM(0.2) ~~ B(4) .762 17 19.4 68.4 5.9 TGBM(0.2) 5.9 E(3) ~ .762 18 19.4 68.4 5.9 EGBM(0.2) 5.9 E(4) .762 Examples 11 and 12 were the same as Example 10 with the exception that the level of surfactant was varied. .

In Example 13, no surfactant was used.

The absence of an effect from these variations upon the foamed density is ~.

shown in Table III.

TA8LE III . : : ~.

Foam Density of Examples 10-13 :~ Surfactant CFoam Density Example ~wt. %)(g/cc~ 4 0.51 :~ 11 2 0.53 12 1 0.51 13 0 0.53 Example 19 To 1500g of the uncured adhesive solution described in Example 6 was added 105g of glass bubbles i .~ . . ~ . .

-` 1 3 ~ 3 -23(Product #B-22-AS, 3M~ with mechanical stirring. The suspension was frothed in 96:4 ratio with surfactant E, coated and cured according to the general procedure.

Example 20 To 900g of the uncured adhesive solution described in Example 6 was added 63g cross-linked polyvinylpyrrolidone (#85,648-7, Aldrich Chemical Company) with mechanical stirring.

The resulting suspension was 10 frothed, coated and cured a~ccording to the "General Procedure" in a 96:4 ratio with surfactant E.

Example 21 ` To a mechanically stirred solution of 875g of 15 glycerin, 375g of H2O, 500g of acrylic acid, 120g of lithium hydroxide, 6.0g of triethylene glycol bis-methacrylate, l.Og of Irgacure 651 and l.Og of~methyl ;

hydroquinone, an antioxidant hereinafter referred to as MEHQ, was added 50g of sodium carboxymethyl cellulose (Type ~ 20 7H, Hercules). The resulting solution having a viscosity of 6500 cps at 25C was frothed, coated and cured according to the General Procedure in a 96:4 ratio with surfactant E.

Example 22 -~ To a mechanically stirred solution of 720g of glycerin, 720g of H2O, 400g of acrylic acid, 2.0g of Irgacure 184, 120g of lithium hydroxide and l.Og of MEHQ was added 60g of low viscosity chitosan (Protan Laboratories, Inc.).

The resulting solution having a 30 viscosity of 2000 cps was frothed, coated and cured according to the "General Procedure in a 96:4 ratio with surfactant E.

Example 23 The uncured adhesive solution described in ~ Example 14 was frothed according to the "General Procedure" in a 96:4 ratio with surfactant E and was coated in two ~33~5~3 -240.015" layers with a spun-bonded nylon fabric (1.0 oz., Cerex) sandwiched between the layers.

The resulting multi-layer coating was cured according to the "General ~ ~.

Procedure".

The properties of the adhesives prepared in Examples 1-23 and Comparative Example A are shown in Table IV, below.

,.

' ' ~ ' ~: ' '', .~' , 133~03 ~ C u~ D C J O o ~ g _~ _I O ~ u~ r~ O c~ o~ c~ `D ~ ~ ~ ~ CO ~ O` ~ ~ O~ ~ ~ ~ O _~ _I O O O o~ ~o O O ~o O ~ . ., C ~ O O O O O ~ 1 0 1 1 0 --~ --I O '`` ' C C "~.~.. "','.~.~ u~ ~1 _ ~ o O O `* a~ ,c c ~ ~ o o ~ ~ I~ c~ 0 ~ri 0 ~i O~ C~J 0 ~C i:4 U ~ ~ c~ 0 ~t 0 ~ ~ ~ C ~ u o ~ ~1 u~ ~D ~ ~ ~ ~ ~ ~ ~ ~D 0~ 0 ~ ~ ~ ~ Yl ~ ~ _~ -' ' ~"'~'`'''' ~o ~ I~ o I ~ ~ ~ ~ o r~ o '..... ' ~ C U ~ ~ c~ ,, "~,. ", :

o ~ ~ u~ ~ c l ~ , ~ a~ I ~ ~ I I I I O ~ O c~ 1~ 0 ~D :

L~ 6 a I l~ ~ O n ~ ~ ~ ..

~ wc ~C -- ,' :~ C c~ ~ ~ ~ co o ul u~ o ~ ~ co u~ N ~ CO O ~ ~1 ~ ~ C ~ ~ ~ O O ~ 0 C~ 0 b C~ ~' ~ O Ul , ~ I . ~1 ~J ~ O~ O ~ ~ 0 a~ 6 O O ~1 -tLI ~ ''~' ', ' ':

~ N ~ O ~ ~ I~ C`~ ~7 r~ O _I ~ 00 ~ cr~ O~ ~O ~`J x o I ~ O ~ co ~ O ~ ~ ~ ~33Q~3 -26Example_24 A sample was prepared as described in Example 6 with the following modification. D~ring the coating process, the froth was coated directly onto the 0.01 inch 5 thick polyurethane backing film described in the "General Procedure", and covered with a transparent low-adhesion liner. The General Procedure for curing provided a foamed adhesive with a polyurethane backing on a low-release liner. In this case, the additional step of laminating a lO backing to the cured adhesive was eliminated.

" ' ':

Example 25 A foamed pressure-sensitive adhesive in which the hydrophilizing component is covalently bonded into the 15 polymer network can be prepared by the following procedure~ To a solution of 300 g of Thickener I, 100 g of acrylic acid, 5.0 g of TGBM and 2 g of Irgacure 651, add 6~0 g of a polyoxyalkyleneacrylate. (A polyoxyalkyleneacrylate can be obtained by adding dropwise, 155 g of 20 2-isocyanatoethylmethacrylate to a nitrogen purged solution of 4 drops of dibutyltindilaurate and 2170 g of an amine-functional poly(alkylene oxide) having the formula ( CH30CH2CH2O( CH2CH2)n ( CH2 ( CH3 ) CHO)mCH2 ( CH3 ) CHNH2 where n/m , 2/32, (available as Jeffamine M-2005 from the Texaco ~ 25 Chemical Company), and heating to 35C for 2 hours.) The ~ resulting adhesive premix solution is frothed, coated and cured and the resulting film is laminated to a 0.025 mm polyurethane film as described in the General Procedure.

.

Examples 26-31 In Examples 26-31, earlier examples were repeated with the exception that a different backing or no backing was used when the MVT of the adhesive was tested.

.

Example 26 A sample was prepared as described in Example 6 except that the backing lamination step was omitted.

The ~' r: ~ i~ ~3~0'~03 -27final product consisted of a foamed adhesive layer between two low-adhesion liners. Removal of both liner films at the time of application provided a dressing which was tacky on two sides and was suitable for attachment of additional 5 devices such as an ostomy or exudate collective device.

Example 27 ..

A sample was prepared as in Example 6, except a rayon non-woven web as described in U.S.

Patent 3,121,021 10 to Copeland, the backing u~ed in MicroporeTM brand tape (3M), was substituted for the polyurethane film in the backing lamination step.

Example 28 A sample was prepared as described in Example 3 except that the backing lamination step was omitted. -~ : : .

Example 29 A sample was prepared as described in Example 4 20 except that the backing lamination step was omitted.

Example 30 -A sample was prepared as described in Example 1 except that the backing lamination step was omitted.

Comparative Example B .

A sample was prepared as described in Comparative Example A above, except that the backing lamination step was omitted. - ;

~0 ` ~:

.

1330~03 -28TAsLE V Effect of Backing on MVT MVT Example IOA/AA/PPGBacking* (g/m2-24 hr) 6 -- I 921 26 -- none 3476 27 -- II 3219 3 40/20/40 I 299 10 28 40/20/40 , none 447 ;

4 35/25/40 I 266 29 35/25/40 none 566 1 22.5/22.5/55 I 477 22.5/22.5/55none 531 A 9 0/10/0 I 207 B 90/10/0 none 329 * Backings~ I: 0.025 mm polyurethane film II: non-woven rayon web The data shown in Table V illustrate the general superiority, in terms of MVT, of the adhesives of this invention as compared with adhesives of the type shown in Comparative Examples A and B.

Example 31 In order to confirm the impermeability to liquid water, the adhesive described in Example 23 was evaluated by the following procedure. The apparatus used consisted of a pres~ure loop made of copper tubing, 4.13 cm in 30 diameter. One end of the loop was connected to a source of compressed air and was fitted with a pressure regulator.

The opposite end of the loop had a flat rigid flange of 7.6 ~ outer diameter and 3.6 cm inner diameter with a rubber O-ring of 4.4 cm diameter embedded in the flange for 35 sealing. A matching top ring was used to clamp the test ~ ` samples in place.

.

~ 3 ~ 3 '~ -29- ;

The pressure loop was fitted with a solution of ~ 692 parts deionized water, 7 parts DOWFAXTM 2A1 surfactant available from Dow Chemical Co., and 0.7 parts methylene blue dye.

The adhesive sample with both low-adhesion 5 carriers removed, was laminated to a single layer of Whatman 4-Qualitative filter paper.

With the filter paper side facing away from the dye solution, the test sample was ` '-~ secured between the two flanges of the apparatus described ' '~ above, and the apparatus was rotated to exclude air between ' ' 10 the sample and the dye solution. Air pressure of 76.2 cm of water was applied for two'minutes at which time no ~ evidence of dye solution wetti~g the paper was observed.

The air pressure was increased until the'fi'l'ter paper split ;~ due to expansion of the adhesive; still no evidence of 15 wetting of the paper was observed which indicated that the foamed adhesive sample was not permeable to liquid water.

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