JPH02211145A - Treating article - Google Patents

Abstract

PURPOSE: To obtain a high drape in a wound/burn treatment supply, by forming a crosslink gel of a pressure-sensitive adhesive from a solution or dispersion of a water-soluble synthetic polymer dissolved or dispersed in water or a plasticizer. CONSTITUTION: A return padding 10 for electrosurgery is composed of an electroconductive member 12 and an electroconductive, water-insoluble, hydrophilic and elastic pressure-sensitive adhesive 14. The padding 10 is prepared by coating a foam layer 22 with an adhesive layer 26, laminating a nonwoven fabric layer 24, placing the electroconductive member 12, coating a no- crosslinked proper synthetic polymer dissolved or dispersed in a proper plasticizer on the nonwoven fabric layer 24 and the the electroconductive member 12, crosslinking by ionic irradiation, then placing a release liner 28. Thus, a product with higher drape ability than skin can be obtained, which allows passage of oxygen, moisture, drugs and salts soluble to the adhesive, and functions as a barrier for bacteria.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel dressing, and more particularly to a dressing using a pressure-sensitive adhesive that is insoluble in water, hydrophilic, and elastic.

Hydrophobic materials consisting of polymers are most typical of the conventional pressure sensitive adhesives used to secure substrates to the human body. Many adhesive bandages are made by using a variety of such adhesives in thin film form. Such hydrophobic polymeric materials are often made by homopolymerizing or copolymerizing one or more vinyl-based monomers, such as acrylic esters, methacrylic esters, vinyl alcohols, or vinyl esters. Natural rubbers and rubber-like substances are sometimes used in conventional adhesive compositions.

EKG monitor electrodes (EKGmonHor
When fixing a device such as an adhesive or a bandage, removing the adhesive often causes trauma to the skin to which the adhesive has been adhered, causing discomfort and pain. This type of injury can also lead to hair pulling, scarring, erythema, swelling, chicken pox, epidermal peeling, or skin lacerations. Discomfort and scarring are exacerbated when the adhesive remains in contact with the skin for extended periods of time. Often, EKG monitor electrodes and post-surgical dressings remain on the patient's skin for -weeks, sometimes longer. Thus, removal of conventional bandages and electrodes is often very painful and remains painful for some time.

Pressure-sensitive adhesives made of hydrophilic polymers have also been known. This type of adhesive has much lower K-generality than hydrophobic pressure-sensitive adhesives. Among the major uses of hydrophilic pressure sensitive adhesives are colostomy adhesives and conductive adhesives for fixing electrodes to the human body. These pressure sensitive adhesives are much less likely to cause skin damage than hydrophobic adhesives.

Some hydrophilic adhesives are made by chemically crosslinking polymeric substances. Examples of this type of prior art are U.S. Pat. No. 3,998,215 to Anderson et al.
), U.S. Pat. No. 4,215,110;
nes) for UK patent @2034184, Velve (B
No. 4,086,078 to Kater, and US Pat. No. 4,094,822 to Kater. The adhesives disclosed in each of these patents are used as patient electrodes and are either themselves electrically conductive or rendered electrically conductive, such as by bonding strands of electrically conductive material together using the adhesive. The Anderson et al., Hymes, and Catter patents state that the adhesive is formed from an aqueous solution of a polymeric material.

In the Anderson et al. patent, a porous web-like material is soaked in an aqueous solution of a hydrogel-forming agent (e.g., polyvinyl alcohol) to wet the web-like material, excess solution is removed, and the web-like material is The web-like material is immersed in a solution of a gel-forming agent or cross-linking agent for hydrogels in order to form a hydrogel throughout the web.

It is stated that the hydrogel thus obtained has low adhesion to the body surface but sufficient cohesiveness so that it does not remain when removed.

The Heims patent relates to a conductive adhesive having a conductive adhesive containing a hydrophilic polysaccharide material (Karaya), an alcohol (glycerin) to impart plasticity, an electrolyte salt and propylene glycol. Another embodiment of the adhesive includes additive materials for crosslinking the hydrophilic polysaccharide material. It is stated that such chemical crosslinking agents include gelatin, polyvinyl acetate, certain polyesters, and calcium salts.

Hymes' UK patent application is similar to Hymes' above US patent. The adhesive described in the British patent application is formed from dry Karaya gum powder and a non-volatile liquid with an inic salt or finely divided silver or aluminum. In one of the embodiments, the adhesive is a 15-70% aqueous solution of polyacrylic acid (25% concentration), Karaya 1
5-45% water, 10-35% water, 0-35% isopropyl alcohol, and 1-3% electrolyte. Additives for chemically crosslinking Karaya are mentioned to include polymers such as vinyl acetate-ethylene copolymers and polyacrylic acid. Also, page 7, No. 48-
Line 50 states that the substrate compound may be subjected to radiation to inhibit the growth of microorganisms and that such radiation should be gamma rays below 2.5 megarads.

The Kata patent relates to electrodes with adhesive-electrolyte materials. Polyvinyl alcohol adhesive is said to be preferable, and as this type of adhesive, polyvinyl alcohol adhesive with a polymerization degree of 1700 and 88
% hydrolyzed polyvinyl alcohol 15-25%
and a composition in which 5-10% glycerol is present. Suitable adhesive-electrolyte materials are those based on polyvinylpyrrolidone (PVP), polyacrylamide or polyvinylpyridine.

The above-mentioned Berb patent also relates to an electrically conductive, hydrophilic adhesive comprising a chemically crosslinked hydrophilic copolymer composition. The starting materials for preparing this copolymer composition are, for example, (a) α.

These are an ester of a β-olefinically unsaturated carboxylic acid and a monohydric or polyhydric alcohol having a quaternary ammonium group at the terminal, and (b) an α,β-olefinically unsaturated comonomer.

Other references relating to adhesive JJ used in patient electrodes include Larimore, UK Patent Application No. 2045088, Sakurada et al., UK Patent Application No. 4237.
No. 886, U.S. Pat. No. 4,243,051 to Wlttetnan, Bailey
), U.S. Pat. No. 4,243,053, by νar
U.S. Pat. No. 4,248,247 by e) et al.
U.S. Pat. No. 4,267,840 to Paine et al., U.S. Pat.
U.S. Patent No. 356,505 to Hauser et al.
No. 9, U.S. Patent No. 3 by Adolph et al.
No. 607788, Relnhold
U.S. Pat. No. 3,911,906 by Wate
U.S. Pat. No. 3,993,049 by R), Burton (B
U.S. Patent No. 4,008,721 to Reichenberger, U.S. Patent No. 4,016,869 to Reichenberger, Burton
U.S. Pat. No. 4,087,342 by Lar
U.S. Pat. No. 4,141,368 by Cross et al.
U.S. Pat. No. 24,908, reissued by Ulrich et al., U.S. Pat.
No. 3,285,838 by Man) et al.
It will be done. Of these patents, the Larimore UK patent application and the Sakurada, Wichman, Bege, Ware, and Leather patents are believed to relate to adhesives based on crosslinked polymers. The Reinhold, Larimore, Burton, Cross et al. patents relate to acrylic polymer based adhesive materials. Among these patents, the Reinhold patent disperses conductive particles throughout the adhesive material. This kind of adhesive layer has uneven conduction of electricity, low conductivity, high manufacturing cost, difficult to manufacture, poor adhesion, cannot absorb sweat and retains a small amount of moisture. The mere presence of these substances tends to cause a loss of adhesive strength.

In the aforementioned patent to Cutter, PVP-based adhesives are disclosed as being suitable. The patent by Gutman et al. relates to an electrolyte composition consisting of an aqueous solution of sodium chloride, preferably fully saturated with silver chloride, and containing up to 7.5% polyvinyl alcohol as a thickening agent. is considered preferable. It is also stated that borax may be used to aid the thickening effect of polyvinyl alcohol.

Other patents related to chemically crosslinking aqueous solutions of polymers include U.S. Pat. No. 3,087,920 by Suzumura et al.
No. 4,036,808 to Rellbaun et al., Caldwell et al.
U.S. Pat. No. 3,932,311 to I) et al., U.S. Pat. No. 28,188 to Azorlosa
No. 18, U.S. Patent No. 4,089,832 to Yamauchi et al., U.S. Patent No. 3 to Wichterle
No. 220,980, US Pat. No. 3,545,230 to Horse, US Pat. No. 3,316,129 to Herrett et al., and So.
U.S. Pat. No. 2,838,421 by h I ).

Among these, the patent of Suzumura et al. relates to polyvinyl alcohol soluble in cold water and has a hydrolysis rate of 75 to 9.
It contains a mixture of 0% partially saponified polyvinyl alcohol, a bleaching agent consisting of diaminostilbene, and a surfactant. Column 3 of the patent, No. 3
In lines 3-35, the partially saponified alcohol is
It is stated that it is thought to react with diaminostilbene in water to form three-dimensional crosslinks to produce a gel, and column 3, line 47 states that polyvinyl alcohol, which is soluble in cold water, is useful as an adhesive. It is stated that.

The Lehmbaum et al. patent also relates to conductive hydrogels obtained by reacting cationic polyelectrolytes with gel-forming polymers such as polyvinyl alcohol, polyacrylic acid, or polyesters. In column 8, lines 19-22 of that patent, it is stated that hydrogels with a crosslinked structure can be prepared from an aqueous solution of a mixture of polyvinyl alcohol and polyacrylic acid or polyhydroxylethyl methacrylate. The gel described in this patent is believed to be an adhesive.

The Caldwell patent referred to above relates to conductive adhesive compositions containing crosslinked acrylates and/or methacrylates and silver particles. The Azorrosa patent also relates to a method for making coated papers using polyacrylamide or acrylamide-acrylic acid copolymers as adhesives. In its preferred embodiment, the coated paper is treated with a crosslinking agent to make the adhesive highly insoluble and to increase adhesive strength.

The above patent by Yamauchi et al. relates to a hydroplastic composition which can be obtained by subjecting a water-soluble polymer (polyvinyl alcohol, polyacrylamide, PvP, etc.) to a crosslinking reaction and then crushing the crosslinked product. Contains granular gel.

It is believed that ionizing radiation may be used to promote crosslinking. This plastic composition is suitable for producing molding materials with low flammability.

The Uichterle patent also relates to hydrogels consisting of crosslinked hydrophilic polymers and 20-97% aqueous liquid. The hydrogel can be shaped by cutting or other means into, for example, lenses, pessaries, dialysis membranes, and the like. It is believed that medically active substances, such as antibiotics, can be dissolved in the aqueous structure to provide treatment over a long period of time.

The above Morse patent relates to a flexible cooling device comprising a reinforcing layer of insoluble hydrophilic gel. If desired, the gel contains substances to control physical and chemical properties such as freezing temperature and chemical stability. Examples of starting materials for preparing gels are polyethylene oxide, pvp, polyacrylamide, polyvinyl alcohol, maleic anhydride-vinyl ether copolymer, polyacrylic acid, ethylene-maleic anhydride copolymer, polyvinyl ether, polyethyleneimine, polyvinylalkylpyridinium. halide and polymethacrylic acid. Insolubilization is promoted by ionizing radiation or chemical crosslinking. The resulting gel must be capable of holding relatively large amounts of liquid. Water can also be used as the only liquid, and
It is believed that other liquids such as alcohols can also be used, and mixtures of water and other liquids or solutes can also be used. - If it is desired to use more gel layers, a film of inert material such as polyethylene or metal foil is used to separate the gel layers and prevent them from adhering when stacked.

The patent by Herrett et al. is directed to a plant growth medium containing an active agent and a water-insoluble, crosslinked polymeric material that serves as a matrix for the active agent. Examples of such polymeric materials include polyvinyl alcohol, pvp, polyacrylic acid, polyvinyl acetate, polyacrylamide,
and vinyl alcohol-vinyl acetate copolymers. The polymeric material is crosslinked chemically or by irradiation with ionizing radiation. The irradiation is carried out in the solid phase or in solution, for example using water as solvent. In one embodiment, a homogeneous aqueous solution of the polymeric material is prepared and then irradiated for a sufficient period of time to form a gel-like material and to dehydrate the gel-like material. As activators, quaternary ammonium salts,
Copper sulfate, antibiotics, and propylene glycol insect repellents are mentioned. In column 10, lines 39-44 of the patent, it is stated that the roots of plants growing in soil compositions containing cross-linked polyethylene oxide were attached to particles of the polymer matrix.

The Saul patent also relates to an adhesive tape having a water-insoluble adhesive composition comprising a solid, water-soluble polyvinylcarboxylic acid (e.g., polyacrylic acid) and a compatibility therewith. It consists of a blend with a hydroxy-polyalkylene system having permanent plasticity (for example, polyethylene glycol or polypropylene glycol). Another example of polyvinyl carboxylic acid is a 50/50 copolymer of polyvinyl methyl ether and maleic anhydride. The internal strength of the adhesive has been increased by including chemical crosslinkers in the adhesive mixture. It is thus stated that the cured adhesive has greater resistance to water, but dissolves in water by mechanical stirring or mixing.

In addition to the Morse and Herrett patents mentioned above, N-
Prior art related to vinyl-2-pyrrolidone-based hydrogels includes Stackler
), U.S. Pat. No. 3,878,175 by Ho.
US Pat. No. 3,759,880 to f fmann et al. and US Pat. No. 4,226,247 to Hauser et al. Among these patents, Stella Fuller's patent concerns a polymeric material that is highly spongy and is characterized by swelling in water and becoming pliable when wet.

This sponge-like polymer is obtained by copolymerizing and partially crosslinking 30-90% by weight of N-vinyl lactam monomer and 10-70% by weight of acrylate monomer. Thus, the sponge-like polymeric materials are used in various industries, in human cosmetics, and as sterile dressings for wiping and absorbing pus, blood, and other body fluids during surgical procedures. is said to be suitable. The Hoffman et al. patent also relates to the production of insoluble, slightly swellable poly-N-vinylpyrrolidone-2. The polymeric materials of this patent are said to be suitable absorbents for many uses, and are particularly effective as beverage clarifying agents.

The Hauser et al. patent discloses that adhesives (preferably PVP
The present invention relates to an electrode having a The adhesives are obtained by mixing an active agent such as PVP with a plasticizer (eg dioctyl phthalate, camphor or glycerin) or a conventional tackifier.

The Herrett et al., Yamauchi et al., and Morse et al. patents mentioned above describe the use of radiation to crosslink polymeric materials. Similarly, Dauben: ] (
US Pat. No. 3,897,295 to Dovbenko; US Pat. No. 3,264,202 to King
No. 29, U.S. Patent No. 29 by Graham
No. 84455, O'Driscoll (0' Driscoll)
U.S. Pat. No. 3,841,985 by L) et al. and U.S. Pat. No. 411 by RestaInO
No. 5339 is concerned with irradiation of polymeric materials.

In the Daubenko et al. patent, irradiation is carried out in a solvent-free solution or approximately solvent-free solution of the polymer dissolved in a heptamer. The King patent also relates to the production of gel-like materials by irradiation treatment of polymers of ethylene oxide. The gel-like materials of that patent are said to be useful as wetting agents.

The O'Driscoll et al. patents mentioned above relate to irradiation of solid dry materials containing PvP, and the Graham patent uses irradiation to modify solid products obtained from alkylene oxide polymers and polyvinyl ethers. It's about things. Thus, column 3, lines 59-61 of the Graham patent describes soaking benzene-soluble polytetramethylene oxide in water prior to irradiation. In the Restaitz patent, an aqueous solution of water-soluble and nil monomers is irradiated for the purpose of obtaining a high molecular weight water-soluble polymer.

According to the present inventor's knowledge, the above-mentioned prior art and other prior art are all water-insoluble, hydrophilic, elastic pressure-sensitive adhesives that are transparent and flexible. is extremely high in moisture and exhibits a flexible but strong, rubbery solid that does not squeeze out when it absorbs moisture; Additionally, there is no disclosure of adhesives that are permeable and provide a barrier to bacteria.

Such adhesives may be useful as coatings on web-like supporting substrates. Web-like substrates coated with the adhesive are used as bandages, burn and trauma dressings, colostomy devices, bedsore pads, sanitary napkins, diapers, and also in shoes, battens, casts, and orthopedic devices. It could be used as a vibration- or shock-absorbing material, used as padding in sports, as a padding for sports, as a sound-absorbing material, or as a vehicle for delivering medicinal ingredients.

Additionally, self-supporting layers with such adhesives can be used for similar purposes and are also useful as cosmetic facial masks and for securing mammalian prosthetics and costumes. used for. Certain of such novel adhesives are electrically conductive and can serve to attach the electrically conductive member of the electrode to a particular surface, such as mammalian tissue.

It is thus an object of the present invention to provide a dressing using a water-insoluble, hydrophilic, elastic and pressure-sensitive adhesive. Thus, the adhesive used in the present invention absorbs moisture without wringing it out; it is transparent, ultra-flexible, and soft, but strong and rubbery. It is a solid substance that acts as a barrier to bacteria; it is also permeable to oxygen, moisture, and chemicals and salts that are soluble in the adhesive.

It is therefore an object of the present invention to provide a burn or wound dressing supported by a web-like substrate and having a layer of adhesive as described above.

Other objects and effects of the present invention will become apparent from the following description.

To achieve the above object, the present invention provides a water-insoluble, hydrophilic and elastic adhesive comprising at least one synthetic organic polymer crosslinked by radiation and an adhesive plasticizer. A pressure adhesive is provided. The adhesive plasticizer is present in an amount sufficient to maintain the elastic (elastomeric) state of the adhesive. The crosslinked polymer is insoluble in water and has a three-dimensional matrix;
It is formed from a solution or dispersion of at least one suitable non-crosslinked synthetic polymer with gel-forming properties in a solubilizing plasticizer. The solubilizing plasticizer is compatible with the crosslinking effect of radiation, and the ratio of the solubilizing plasticizer to the non-crosslinking polymer is such that the gel formed by crosslinking retains the solubilizing plasticizer within the three-dimensional matrix. Adjust the ratio as much as possible. The same type of plasticizer may be used, or several different types of plasticizers may be used, and at least one type of substantially non-volatile elastic agent is included. The elastomeric agent is present in an amount sufficient to maintain adhesive properties when the adhesive plasticizer is substantially elastomeric. Such adhesives according to the invention are useful as coatings on adhesive-supporting substrates in the form of webs, and are also useful as self-supporting layers.

The present invention will be described below along with the best mode for carrying out the invention.

As mentioned above, the present invention relates to novel pressure sensitive adhesive dressings. The adhesive used in the present invention is a water-insoluble, hydrophilic, and elastic pressure-sensitive adhesive;
It is a soft but strong rubbery solid, which is further characterized by being transparent and ultra-flexible. In fact, the adhesive used in the present invention has better drape properties than the skin itself.

The adhesive used in the present invention absorbs moisture and the moisture is not squeezed out. The adhesive is permeable to oxygen, moisture, chemicals or salts that can be dissolved in the adhesive, and also acts as a barrier to bacteria.

The adhesive used in the present invention adheres cohesively to the skin, but does not exhibit adhesion to hair, and is therefore difficult to remove when removing the pressure-sensitive adhesive-coated substrate from areas of the body where hair is present. Reduces discomfort. The adhesive used in the present invention can remain on the human body for hours, even days, without causing skin bleaching or wrinkling.

The adhesive used in the present invention is capable of absorbing significant amounts of moisture without substantially reducing its adhesive strength. In this regard, the adhesive used in the present invention has properties that allow it to absorb and permeate perspiration, including moisture, salts, urea, ammonia, and other exudates as it leaves the surface of the skin. has. The adhesive can be prepared to contain significant water, or it can be prepared in a dehydrated state, thus providing even higher moisture absorption capacity. The "dry" adhesive used in the present invention has a surprisingly high oxygen absorption capacity, as shown in Example 1 and Table 1.

(The meaning of the term "dry" will be explained below.) The presence of a significant amount of aqueous phase in the adhesive is also expected to further increase the oxygen absorption capacity.

Adhesives used in the present invention are often superabsorbent. Here, superabsorbent means that the adhesive absorbs an amount of water approximately equal to its own weight without loss of adhesive strength.

The adhesive will not be superabsorbent if the plasticizer is essentially polypropylene glycol or a copolymer of 25 mole % ethylene oxide and 75 mole 26 propylene oxide (e.g. Ucon 75 from Union Carbide Company). -1,190,000). For many of the adhesive applications described herein, it is advantageous for the adhesive to be superabsorbent. However, when used in colostomy devices, or perhaps as a medicinal ingredient delivery vehicle (in this case potash, depending on the solubility properties of the medicinal ingredient, the adhesive is absorbent but superabsorbent). It is preferable not to, and therefore plasticizers as mentioned a little earlier should be used.

The adhesive used in the present invention can filter microbial contaminants by providing an enclosure through which bacteria can flow. As a result, the provision of antibiotics in wound dressings will often be unnecessary. The adhesive of the present invention has fluid permeability and bacteria-retaining properties very similar to human skin, so it appears to provide immediate wound healing to prevent infection. It is thought that the formation of scar tissue is slowed down.

Furthermore, in one embodiment of the invention, the adhesive is electrically conductive and is particularly suitable for use as an electrode.

In FIG. 1, an electrosurgical return pad is illustrated. The pad consists of a conventional conductive member 12 and a conductive, water-insoluble, hydrophilic, elastic pressure-sensitive adhesive 14 according to the present invention. Also shown in the figure is arm 1B, which serves as the surface to which electrosurgical return pad 10 is attached.

Also shown in FIG. 2 is a bandage 17 comprising a web-like support substrate 18 and a layer 20 of the adhesive of the invention coated onto the substrate. Bandages, sanitary napkins, burn or wound dressings, colostomy devices according to the invention,
Bed sore pads, vibration or shock absorbers such as pads, sound absorbers, and medicinal ingredient delivery media generally have a structure as shown in the figure. However, the size and thickness of substrate 18 and adhesive layer 20 will vary depending on the application.

FIG. 1 shows foam layers 22 and 23, a nonwoven fabric layer 24,
Also shown are adhesive layers 2B and 27, release liners 28, 30 and 32, and electrical connection holes 34.

These configurations of pads are conventionally known. Adhesive layer 2B bonds nonwoven fabric layer 24 to foam layer 22. Foam layer 22 is comprised of polyethylene foam, as is conventionally known, and nonwoven layer 24 is comprised of a polyester material (e.g., Burlington).
It is suitably constructed from a polyester material such as NexuS (trade name) sold by Ington. After removing the release liner 28, the pad 10 is attached to the arm 16.

An advantageous method for manufacturing pad 10 is to form foam layer 22.
is coated with an adhesive layer 2B, and a nonwoven fabric layer 24 is applied on the adhesive.
are placed on the nonwoven fabric layer 24 to form a laminate, the conductive member 12 is placed on the nonwoven fabric layer 24, and a suitable non-crosslinked synthetic organic polymer is dissolved or dispersed in an appropriate plasticizer to form a laminate. The method consists of coating the conductive member 12 and subjecting the obtained laminate to ionizing irradiation. Next, release liner 28 is placed. Synthetic organic polymers and plasticizers will be described later.

In FIG. 3, a self-supporting layer 3B according to the invention is shown. In all cases where the adhesive of the present invention is used in a self-supporting layer, it will generally have a structure as shown, although the size and thickness of layer 36 will vary depending on the particular application. This self-supporting layer with adhesive preferably has a thickness in the range of about 3 to 6 #l1m. Of course, when used in a self-supporting layer, the adhesive may be sandwiched between a pair of conventionally known release liners.

The adhesive used in the present invention does not contain at least one synthetic organic polymer crosslinked by radiation and an amount of adhesive plasticizer sufficient to maintain the elastic (elastomeric) state of the adhesive. The preparation of the crosslinked polymer involves dispersing or dissolving a gel-forming, non-crosslinked synthetic organic polymer in a plasticizer having the same or different composition as the adhesive plasticizer, and then adding an appropriate amount of the gel-forming, non-crosslinked synthetic organic polymer to the resulting dispersion or solution. This is done by applying irradiation. With the appropriate amount of irradiation,
An adhesive is obtained having properties as described herein. Thus, adhesives made of crosslinked polymers are water-insoluble and have a three-dimensional matrix structure.

Suitable non-crosslinked synthetic organic polymers include carboxyvinyl monomers, vinyl ester monomers, esters of carboxyvinyl monomers, vinylamide monomers, hydroxyvinyl monomers, cationic and amine- or quaternary ammonium-containing monomers as repeating units. It contains vinyl monomer or N-vinyl lactam monomer. Other suitable non-crosslinked polymers are homopolymers or copolymers of polyvinyl ether,
Alternatively, it is a copolymer derived from a half ester of maleic anhydride. The polymer may be used as a polymer formed from a mixture of monomers that are compatible with each other, for example a mixture of N-vinyl lactam monomer and carboxyvinyl monomer. Additionally, a suitable amount of mutually compatible non-crosslinked polymers; for example, about 11.25 weight percent polyvinyl alcohol (hydrolysis rate 88%).
) and about 3.75 weight percent polyacrylic acid (molecular weight about 450,000). Suitable non-crosslinked polymers are water-soluble, for example those having repeating units derived from carboxyvinyl monomers, homopolymers or copolymers of polyvinyl alcohol, or approximately equal amounts of methyl vinyl ether and maleic anhydride. It is a copolymer formed from.

Preferred non-crosslinked polymers include those having repeating units derived from N-vinyl lactam monomers. Examples of N-vinyllactam monomers are N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and mixtures thereof. Suitable polymers derived from N-vinyl lactam monomers include N-vinyl-
2-Pyrrolide homopolymer or N-vinyl-2
- a copolymer of pyrrolidone and nil monomer,
In the latter case, the vinyl monomer is compatible with the solubility or dispersibility of the non-crosslinked polymer in the dissolving or dispersing plasticizer and with the solubility or dispersibility of the crosslinked polymer in the adhesive plasticizer. be. Vinyl monomers of this type include vinyl acetate and esters of α,β-olefinically unsaturated carboxylic acids and amino group-containing alcohols. If the vinyl monomer is vinyl acetate, it is advantageous to set the molar ratio of vinyl acetate and N-vinyl-2-pyrrolidone in such a way that the resulting copolymer is water-soluble.

One example of this type of copolymer that is commercially available is BA
It is sold by SF Company under the trade name Luviskol V A.

Also preferred is a copolymer of N-vinyl-2-pyrrolidone and a carboxylic acid ester such as those described above; in this case,
Preferably, the polymer contains about 20 mole percent ester. In particular, it is preferred that the ester is dimethylaminoethyl methacrylate or a partially or completely quaternized salt of the methacrylate.

A copolymer of N-vinyl-2-pyrrolidone (K value approximately 90) containing a partially quaternized salt has a 20%
It is sold as an aqueous solution under the trade name Gaf'quat 755N. This commercially available copolymer contains 20 mole percent dimethylaminoethyl methacrylate partially quaternized with diethyl sulfate. A preferred polyvinylpyrrolidone has a Pvp of -90 and a G
It is available as NP-90 from AF.

The above “carboxyvinyl monomer” used in the present invention
Examples include water-soluble salts of carboxyvinyl monomers, including, for example, alkali metals, ammonia or amines. Examples of carboxyvinyl monomers include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid and itaconic anhydride, 1,2-dicarboxylic acids such as maleic acid or fumaric acid, maleic anhydride,
Also included are mixtures thereof. A preferred carboxyvinyl monomer is acrylic acid.

When the carboxyvinyl monomer is 1,2-dicarboxylic acid or maleic anhydride, the non-crosslinked polymer includes a comonomer. The comonomer can be, for example, ethylene, propylene, n-butylene or isobutylene.
2 to C4 olefinic monomer; C4 diolefinic monomer such as butadiene; 01 to C4 alkyl vinyl ether such as methyl vinyl ether; or vinyl acetate. The amount of 1,2-dicarboxylic acid or maleic anhydride is substantially equivalent in molar ratio to the comonomer. Vinyl acetate is a preferred comonomer and is used in an amount up to about 20% by weight relative to any other carboxyvinyl monomer.

As the polyvinyl alcohol, one or more water-soluble polyvinyl alcohols are used.

A preferred polyvinyl alcohol is a high molecular weight polyvinyl alcohol with a hydrolysis rate of 88% obtained by hydrolysis of polyvinyl acetate. This polyvinyl alcohol is available from Monsanto under the trade name Ge.
It is available as 1vato120-90.

Radiation-irradiated crosslinked polymers are obtained by irradiating a solution or dispersion of a suitable gel-forming non-crosslinked synthetic organic polymer in a plasticizer.

Here, the plasticizer is water-soluble or water-dispersible, the non-crosslinked polymer can be dissolved or dispersed in the plasticizer, and the water and non-crosslinked polymer can be dissolved or dispersed in the plasticizer. It is something that can be done. As used herein, "solubilizing plasticizer" refers to such a plasticizer. This plasticizer is also compatible with irradiation. Here, "compatible with irradiation" means that the solubilizing plasticizer does not inhibit crosslinking of the polymer caused by irradiation.

Preferably, the solubilizing plasticizer includes at least one substantially non-volatile elastomeric agent and further includes a volatile solvent that, in combination with the elastomeric agent, disperses or solubilizes the polymer. The volatile solvent is an aqueous solvent, a non-aqueous solvent, or a mixture thereof, and in combination with an elastic agent,
The elastomer composition is selected to form an elastomer composition that is capable of dissolving or dispersing non-crosslinked polymers, and to form an adhesive that is capable of dissolving or dispersing crosslinked polymers. Preferably, the volatile solvent is an aqueous solvent, particularly preferably water. When the volatile solvent is water, up to about 90% of the solubilizing plasticizer can be water. A very important feature that distinguishes the adhesive used in the present invention from the prior art is that the adhesive used in the present invention retains its adhesive strength upon removal of the volatile solvent. In contrast, aqueous solvent gels, such as those disclosed in the Stellar Fuller patents, Herrett et al. patents, and the Cutter patents mentioned above, harden and lose adhesion upon removal of the volatile solvent.

The substantially non-volatile elastomeric agent as described above is present in an amount sufficient to maintain the adhesive strength of the adhesive containing the crosslinked polymer when the adhesive plasticizer is formed substantially from the elastomeric agent. do. As used herein, the term "substantially" with respect to plasticizers means that only up to about 2 weight percent of the volatile solvent is present. Suitably, the plasticizer is present in an amount ranging from about 0.5 to 4:1 by weight to crosslinked polymer.

Solutions or dispersions formed from uncrosslinked polymers with solubilizing plasticizers exhibit a clear or hazy appearance. The relative ratios of non-crosslinked polymer and plasticizer are chosen such that the gel produced by radiation crosslinking retains the plasticizer in its three-dimensional matrix.

Preferred as substantially non-volatile elastomeric agents are suitable polyhydric alcohols, mono- or diethers of polyalkylene glycols, mono- or diesters of polyalkylene glycols, amphoteric surfactants consisting of imidacillin derivatives, lactams, N-substituted Lactams, amides, polyamides, amines, polyamines, condensates of polyethyleneimine and shrimp chlorohydrin, polyquaternary ammonium compounds,
or a compatible mixture thereof. It is particularly advantageous to use polyhydric alcohols, which are preferably polyalkylene glycols, especially polyethylene glycols. Other suitable polyalkylene glycols include copolymers formed from about 25 mole percent ethylene oxide and about 75 mole percent propylene oxide. Copolymers of this type are manufactured by Union Carbide.
It is sold under the trade name 75-H90000 by E). Other useful polyhydric alcohols include sorbitol, 1,3-butanediol, 1,4-butanediol, 1°4-butynediol, appropriate glucose derivatives, pentaerythritol, trimethylolethane, glycerin, propylene glycol, 1.3-propanediol, polyglycerin, ethylene glycol, and compatible mixtures thereof. The elastic agent present during the radiation treatment step must be compatible with radiation crosslinking. Thus, for example, glycerin (which tends to reduce the crosslinking effect of radiation) should not be present as an elastic agent in an amount of more than about 5% by weight of the total composition before radiation treatment. (This amount is
(depending on the underlying polymer of the adhesive). When the crosslinking step is finished, glycerin can be present as an elasticity agent and therefore further additions can also be made. It should be understood that where the elastomeric agent is, for example, an amide or amine, such amide or amine should be substantially non-volatile. In addition, as described later,
Elastic agents are generally liquid at room temperature.

Another way to change the composition of an adhesive plasticizer such that the plasticizer contains a volatile solvent is to remove the volatile solvent when the irradiation process is finished.

If the volatile solvent is water, it is preferred to remove some of the water so that only a small amount of water (eg, about 5% or less) is present as part of the adhesive. in fact,
It is highly preferred to remove a sufficient amount of water so that the adhesive becomes "dry" as described below. The advantage of such dehydrated adhesives is that their moisture absorption capacity is greatly increased. Additionally, as shown in the Examples, dehydrated or "dry" adhesives have superior adhesion, significantly better water vapor permeability, and much higher oxygen permeability than "wet" adhesives. As used herein, the term "dry" means having at least dryness as occurs when the adhesive is subjected to air drying at 20° C. for about 48 hours under about 30% relative humidity. "Wet" herein means that the adhesive contains at least about 55% water.

As mentioned above, elastic agents are generally liquid at room temperature.

However, the elastic agent may also become solid at room temperature when freezing point depression is produced by combining the elastic agent with non-crosslinked polymers, other dissolved plasticizers, or suitable additives adapted to the composition before the crosslinking step. be. Although usually solid, suitable non-crosslinked polymers (e.g. with molecular weight of about 4
The substance that causes the freezing point depression in the presence of polyacrylic acid (polyacrylic acid with a molecular weight of about 50,000) is a polyethylene glycol having a molecular weight of about 600 to about 20,000. Particularly advantageous polyethylene glycols for use in the present invention are those having a molecular weight of about 300 or about 600.

Polyethylene glycol (PEG) with a molecular weight of 300 is available from Union Carbide under the trade name Garbovax.
300, and also has a molecular weight of 600.
EG is sold under the trade name Garbovax 800.

In addition, if the remaining components of the plasticizer composition can dissolve or disperse both a mixture of the component and a non-crosslinked polymer and a mixture of the component and a crosslinked polymer, the elasticity of the solid at room temperature Agents can also be used.

As mentioned above, examples of elastic agents are polyhydric alcohols, mono- or diethers of polyalkylene glycols, or N-substituted lactams.

It is very advantageous if the polyhydric alcohol is a polyalkylene glycol, examples of which include polyethylene glycol, polypropylene glycol and copolymers of ethylene oxide and propylene oxide. Suitable mono- or diethers of polyalkylene glycols are polyethylene glycol mono- or diethers, and preferred mono-ethers of polyethylene glycol are polyethoxylated fatty alcohols, polyethoxylated nonylphenols or polyethoxylated octylphenols. Examples of N-substituted lactams include N-cupropyl-2-pyrrolidone, N-(N,N-dimethylamine)propyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone.

Preferably, the non-crosslinked polymer comprises repeat units derived from vinylamide monomers.

Particularly suitable as this kind of 7-summer are α, β
- Amides of olefinically unsaturated carboxylic acids, examples of which include acrylamide and dimethylaminopropylmethacrylamide. Another amide included in this class of amides is methacrylamide propyl-trimethylammonium chloride.

As mentioned above, the non-crosslinked polymer preferably has repeat units derived from carboxyvinyl monomers. When the carboxyvinyl monomer is acrylic acid, the polymer may be a copolymer of acrylic acid and ethylene, vinyl acetate or acrylic ester. A sufficient amount of base is included with the polymer to solubilize the polymer. Here, the base is an amine, a quaternary ammonium or an alkali metal hydroxide. When the carboxyvinyl monomer is maleic acid, preferred comonomers are methyl vinyl ether,
ethylene, vinyl acetate, styrene or butadiene, the amount of the comonomer being substantially equal in molar ratio to the amount of maleic acid.

When the comonomer is styrene or vinyl acetate, a sufficient amount of base is included to solubilize the copolymer.

When the adhesive used in the present invention is prepared from a skin-irritating non-crosslinked polymer or plasticizer, or a non-crosslinked polymer or plasticizer containing a skin-irritating additive, the adhesive may be used in contact with the skin. It is better to use it so that it does not occur.

Examples of polymers of this type are those with repeating units derived primarily from carboxyvinyl monomers (e.g. acrylic acid), and examples of such plasticizers include surfactants or detergents as elastic agents. .

In other cases, the adhesive used in the present invention is hypoallergenic.

Particularly useful elastomeric agents when the non-crosslinked polymer contains repeating units derived from N-vinyl lactam monomers include polyethylene glycols, amphoteric surfactants consisting of imidacillin derivatives, polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated fatty acids, etc. and polyethoxylated octylphenol.

Polyethoxylated octylphenol surfactants are sold by Rohm & Hass under the trade name Tvlton.

Polyvinyl ethers suitable for use in the starting non-crosslinked polymer are polymethyl vinyl ether or polyethyl vinyl ether. Particularly suitable elastic agents include monoethers of polyalkylene glycols or monoesters of polyalkylene glycols.

An example of a monoether of a polyalkylene glycol is polyethoxylated octylphenol, and an example of a monoester of a polyalkylene glycol is a fatty acid ester of polyethylene glycol (eg, monostearate of polyethylene glycol 300). Other useful elastic agents are N-substituted lactams and, of course, polyethylene glycols. N-substituted lactams are also particularly suitable elastic agents for use with non-crosslinked polymers derived from N-vinyl lactam monomers.

If the non-crosslinked polymer has repeat units derived from vinyl ester monomers, the polymer is dissolved or dispersed in the plasticizer prior to the irradiation step and is sufficiently dissolved in the adhesive plasticizer. The polymer contains a suitable amount of comonomer. Examples of such vinyl ester monomers include vinyl acetate and vinyl propionate, and examples of comonomers include N-substituted lactams, vinyl alcohol, hydrolyzed maleic anhydride,
Or crotonic acid. Copolymers containing vinyl esters and vinyl alcohols can be prepared by incomplete hydrolysis of vinyl esters. Copolymers of vinyl acetate and maleic anhydride are prepared by hydrolysis and base treatment. If the comonomer is crotonic acid, a sufficient amount of base is added to dissolve the polymer in the plasticizer prior to irradiation treatment. In this case, the copolymer preferably contains vinyl acetate and crotonic acid in a molar ratio of about 19=1.

When the non-crosslinked polymer is a copolymer derived from a half ester of maleic anhydride, suitable half esters are methyl half esters or ethyl half esters, and preferred comonomers are methyl vinyl ether. C1-C4 vinyl ethers such as, or ethylene.

Other examples of vinylamide monomers are those prepared from α,β-olefinically unsaturated carboxylic acids and diamines (eg, dimethylaminochelamine, aminoethyl-triethylammonium chloride). Examples of hydroxyvinyl monomers used in the starting non-crosslinked polymer include allyl alcohol, hydroxyethyl acrylate and hydroxypropyl acrylate. An example of a cationic vinyl monomer containing amine or quaternary ammonium groups is vinylbenzyltrimethylammonium chloride.

As previously discussed, the relative ratios of uncrosslinked polymer and solubilized plasticizer are chosen such that the gel formed by radiation crosslinking retains the plasticizer within a three-dimensional matrix. The non-crosslinked polymer contains repeating units derived from carboxyvinyl monomers, vinyl ester monomers, esters of carboxyvinyl monomers, vinylamide monomers, hydroxyvinyl monomers, or cationic vinyl monomers containing amine or quaternary ammonium groups. If the solution or dispersion to be irradiated contains about 5
It is preferred to contain 26 to 50% by weight of non-crosslinking monomer. Also, when the non-crosslinked polymer is a copolymer obtained from a half-ester of maleic anhydride, the solution or dispersion advantageously contains about 5 to 50% by weight of the non-crosslinked polymer.

When the uncrosslinked polymer contains repeat units derived from N-vinyl lactam monomers, it is preferred that the solution or dispersion contain about 7-60% by weight of the uncrosslinked polymer. When the non-crosslinked polymer is a polyvinyl ether homopolymer or copolymer, it is preferred that the solution or dispersion contain about 5 to 60 weight percent of the non-crosslinked polymer. If the non-crosslinked polymer is a homopolymer or copolymer of polyvinyl alcohol, the solution or dispersion to be irradiated has a
It is advantageous to contain up to 30 weight percent of non-crosslinked polymer. When the non-crosslinked polymer has repeat units derived from carboxyvinyl monomers, the solution or dispersion contains about 14-20% by weight (preferably 20% by weight).
) of non-crosslinked polymers. When the non-crosslinked polymer has repeating units derived from N-vinyl lactam monomers, the solution or dispersion contains 12.5 to 22.5% (preferably wt.%) of the non-crosslinked polymer. It is especially advantageous. When the non-crosslinked polymer is a homopolymer or copolymer of polyvinyl alcohol, advantageously the concentration of the non-crosslinked polymer in the solution or dispersion is about 7-25% by weight;
In particular, 10% by weight is preferred.

When the non-crosslinked polymer has repeat units derived from carboxyvinyl monomer, a particularly preferred ratio of elastomeric agent to carboxyvinyl monomer is about 1:1 (by weight). When the non-crosslinked polymer is polyacrylic acid, the polyacrylic acid has a molecular weight of about 450,000 to 500,000
It is preferable to have a molecular weight of . Molecular weight is approximately 50,000
0 polyacrylic acid is produced by Gudrich (B, P, Goo
drlch) by Carbopol EX-17
Polyacrylic acid with a molecular weight of 450,000 is sold as a 15% aqueous solution under the name Carbopo1.
It is sold as 907. As previously mentioned, particularly preferred adhesives are in the "dry" state. Removal of the volatile solvent to obtain this adhesive is carried out using the methods described above or equivalent techniques.

When the adhesive comprises radiation-crosslinked polyvinylpyrrolidone and polyethylene glycol (about 300 molecules), the polyethylene glycol is present in an amount of about 0.75 to 1.5 times the polyvinylpyrrolidone on a weight basis. It is particularly preferable to do so. Such compositions, and similar compositions in which polyvinylpyrrolidone is a copolymer of N-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate or a partially quaternized salt of said methacrylate, are disclosed herein. This is a highly preferred composition for use in the invention.

The irradiation dose for producing the adhesive used in the present invention is:
It depends on factors such as the concentration of non-crosslinked polymer in the solubilizing plasticizer and the molecular weight of the non-crosslinked polymer.

For example, when the concentration of non-crosslinked polymer is relatively high or when the molecular weight of the non-crosslinked polymer is relatively large, a relatively small radiation dose is required; When the molecular weight of is relatively small, a relatively large dose of radiation is required. The type of elastomeric agent and the relative proportions of elastomeric agent, other plasticizer components, and non-crosslinked polymer will also affect the amount of irradiation required.

Furthermore, if the irradiation is carried out at a relatively low rate and a free radical scavenger such as oxygen is present, a relatively high dose will be required; on the other hand, relatively long-lived free radicals are likely to be produced. A relatively small amount of irradiation is required when the irradiation is carried out under conditions such as high doses in the absence of oxygen or in solutions where oxygen is rapidly consumed. becomes.

As used herein, the term "irradiation" refers to the irradiation of high-energy radiation and/or secondary energy resulting from the conversion of electrons and other energetic particles to neutrons and gamma rays. These energies are in amounts equal to at least about 100,000 electron volts. Although various types of irradiation such as X-rays, gamma rays, and beta rays are suitable for the purposes of the present invention, radiation produced by accelerated high-energy electrons is convenient and economical. However, regardless of the type of radiation and the type of equipment used to generate it, the ionizing radiation need only have an amount of energy at least equal to about 100,000 electron volts.

Although there is no upper limit to the electron energy that can be applied, the effects required to practice the invention can be obtained without exceeding about 20 million electron volts. - Generally, the higher the electron energy used, the greater the penetration depth into the structure of the material to be treated and the shorter the required irradiation time. For other types of radiation, such as gamma rays and X-rays, energy systems equivalent to electron volts in the range mentioned above are also desired.

The term "irradiation" is defined as "ionizing irradiation" (1on1
z1ng radiation) J, and therefore [
Ionizing electromagnetic wave irradiation
In addition to ionizing particle beam irradiation (OA + agnctic radiation)
article radiation) J.

The term ``ionizing particle irradiation'' refers to the release of electrons or highly accelerated particles such as protons, neutrons, alpha particles, deuterons, or beta particles, which are directed to penetrate into the irradiated material. It is used to refer to something. Charged particles can be used in accelerators with resonance boxes, Van der Graafr generators, betatrons, synchrotrons, cyclotrons, diamadrons and insulated core transformers.
can be accelerated by voltage gradients used in devices such as. Neutron irradiation can be obtained by bombarding certain light metals, such as beryllium, with high-energy positive particles. Particle beam irradiation can also be obtained using nuclear reactors, radioactive isotopes, or other natural or man-made radioactive materials.

"Ionizing electromagnetic radiation" is obtained by bombarding a metal target such as tungsten with electrons of appropriate energy. The energy is imparted to the electrons by using a potential accelerator of over 100,000 electron volts. In addition to this heel irradiation (commonly called You can also get it.

The radiation dose useful for crosslinking non-crosslinked polymers is about 0.
．． 5. ~4.5 megarads, approximately 3.5-4.
An amount of 5 megarads is particularly suitable. This range of radiation doses is particularly useful for compositions consisting essentially of about 18-22% by weight polyvinylpyrrolidone, about 10-70% by weight polyethylene glycol (molecular weight about 300), and water. The resulting adhesive is preferably
It can be rendered electrically conductive by including a suitable amount (e.g. 6-8% by weight) of a conductivity enhancer. It is highly preferred that the adhesive contains about 25-30% by weight PEG 100 and about 20% by weight PVP.

The adhesive used in the present invention optionally contains a compatible preservative such as methylparaben or propylparaben. Mixtures of preservatives may be used, and if a preservative is used, it is used in an amount sufficient to provide a preservative effect. Moreover, the adhesive used in the present invention is FD&CB
It may also contain dyes such as LUE #2.

The adhesive in the present invention is used as a coating on a web-like support substrate. Due to its high cohesive strength, by choosing a suitable substrate such that the adhesion of the adhesive on the web-like substrate is very high, the adhesive used in the present invention leaves no residue when removed. . For example, when polystyrene is used as the supporting substrate, the adhesive exhibits very strong adhesion to polyethylene if the non-crosslinked polymer solution or dispersion is irradiated in direct contact with the polystyrene. A major advantage of the present invention is its great tendency to be reused. As a result, the dressing of the invention can be repositioned several times without losing the performance of the adhesive.

The adhesive used in the present invention has elasticity (elastomer elasticity) and undergoes elastic deformation. When the adhesive of the present invention is subjected to strain, a static restoring stress occurs. Even after being subjected to several hundred percent strain, almost no visible permanent strain occurs when the material is relaxed. This adhesive has very low stiffness, with a stiffness comparable to or lower than that of gelatin desserts.

Since the adhesive used in the present invention is elastic and does not have excessive cold flow properties, the adhesive used in the present invention can be prepared in very thick layers, i.e., approximately 40 mm thick or less. can do.

However, a layer having a thickness of about 3 to 61M is preferred (particularly if the layer consisting of the adhesive is self-supporting) or if a layer of such thickness is applied to the human body when it is stretched. pain is minimized. A self-supporting layer of adhesive can also be coated onto a thick web-like substrate that is not self-supporting, such as gauze or non-woven fabric.

In this case, the web-like substrate would serve to improve dimensional stability and would make cutting the adhesive easier.

A web-like support substrate coated with a layer of adhesive has many uses, and the type of web-like substrate is selected depending on the desired application. Preferably, the web-like substrate is electrically non-conductive.

If it is desired that the coated substrate be used as an adhesive tape, a cellophane membrane, for example, is used as the substrate. Adhesive-coated substrates have numerous uses, such as bandages, burn or wound dressings, sanitary napkins, colostomy devices, diapers, bedsore pads, vibration or shock absorbers, sound wave absorbers, and It is used as a medium for supplying soluble medicinal ingredients to adhesives. In some of these applications, the adhesive includes a medicinal ingredient that is dissolved in the adhesive.

When the adhesive is used as a self-supporting layer, it can be coated onto a substrate for a variety of applications as described above. Furthermore, self-retaining layers of adhesives are useful as cosmetic facial masks and are also used to secure prosthetics and ornaments to the mammalian body.

When the present invention is used in a bandage, the adhesive can replace all three components of a conventional bandage (i.e., adhesive, gauze, and substrate), among other known components. It will be the best. That is, the adhesive used in the present invention as a bandage adhesive does not cause damage, does not pull hair,
It is not painful to use, does not cause discomfort or scarring when removed, and does not retain moisture that can wrinkle the skin as many other adhesives do. . The adhesive used in the present invention also functions as a gauze material, allowing continuous observation of the patient's condition without disturbing the patient.

Since this adhesive is flexible and elastic, it also acts as an excellent padding. Since this adhesive is non-fibrous, it does not adhere strongly to the epidermis, and
It is generally removed without leaving a leprosy scar. This adhesive filters out bacteria and greatly reduces bacterial ingress.

Since this adhesive is elastic in nature, it can be used without the need for a supporting substrate if the thickness is appropriate. The adhesive of the present invention also performs well as a sterile cloth, is able to conform to the most complex shapes of the body, and remains attached even during strenuous exercise. The adhesive of the present invention is highly permeable to oxygen and moisture and is highly preferred as a dressing, particularly as a means of controlling anaerobic bacterial invasion.

This adhesive can absorb fluid drained from minor injuries, so it acts as both an adhesive and an absorbent pad. The advantage this provides is that once a suitably sized sheet is obtained from the adhesive-coated substrate, a package of a specific size or shape can be cut to fit exactly where needed. This is in contrast to conventionally sold bandages, which are made from absorbent pads secured to adhesive tape, which requires adhesive tape of appropriate size and shape.

A problem that often occurs when gauze is used to cover an uneven area is that clotted blood or body fluids tend to coat the fibers of the gauze, resulting in the gauze adhering to the uneven area. In contrast, the adhesive used in the present invention has less tendency to adhere to uneven parts. When used in place of gauze, the adhesive can be formulated to contain a certain amount of moisture ranging from about 0% to 90%, thereby leaving the healing area in a high-humidity or low-humidity environment. Can be maintained in any minute environment.

When used as a burn dressing, the adhesive
It is thought to function as an artificial skin graft to stabilize the patient until a graft of the patient's own tissue can enter the area.

When used as a sanitary napkin, the layer of adhesive can perform all the functions of the three components of the sanitary napkin: absorbent material, adhesive, and support structure. The adhesive of the present invention has the ability to adhere to the cavity, absorb menstrual fluid, and seal the cavity even during strenuous exercise, making it an ideal sanitary napkin. Approximately 4.8 mm (3/16 inch) of adhesive material
If it is made thicker, it can be used alone without a support. If a support is not used, a coating that does not adhere to underwear can be provided by sprinkling talc on one side of the adhesive or treating it with silicone liquid. Since the adhesive used in the invention does not absorb particles, it is advantageous to use a pad of other materials to cover the core of the sanitary napkin.

As a cosmetic facial mask, the adhesive used in the present invention has sufficient flexibility to comfortably cover the entire face. Appropriate amounts of humectants may be added to provide a beauty treatment during sleep, which - by being continued throughout the night, provides a very effective "rejuvenating" beauty treatment. Furthermore,
The adhesive may also contain medicinal ingredients such as those that prevent acne or soothe pain caused by sunburn.

When used as a vehicle for delivering medicinal ingredients,
A layer of adhesive can also be applied to the extrafacial skin. Such applications are particularly advantageous when the medicinal ingredient can pass through the skin. In addition to being able to be applied to the skin, the adhesives used in the present invention can be applied intracavally, rectally, or intravenously, and even subcutaneously to perform subcutaneous treatments. When using the adhesive of the present invention as a drug delivery vehicle, the adhesive is prepared to contain an aqueous solution of a nibutum salt. The user whose feet are coated with the adhesive of the present invention can move around freely,
What's more, you can also "soak" your feet. The adhesive retains the nibutum salt solution and does not release moisture even when compressed. The medicinal ingredient must be soluble in the plasticizer layer of the adhesive and present in an amount sufficient to provide the desired medicinal effect. Examples of medicinal ingredients include hormones such as estrogen, analgesics, and lithium therapeutics. The adhesive used in the invention can also be used as a carrier for depilatory agents.

Adhesives used in the present invention have properties that are useful in treating and preventing pressure sores and bedsores. This is done by applying the adhesive layer of the invention to a specific area of the body, so that friction in that area is felt.

The adhesive used in the present invention can be used as a humectant, a skin conditioner, a depilatory agent, a hormone, a perfume, a cleansing agent, an acne treatment, an antiperspirant, an astringent, an anti-sun agent, and an artificial anti-tan agent. It may also contain beneficial ingredients such as. When used as a medium for supplying an adhesive-soluble medicinal ingredient, the adhesive can perform the function of continuously supplying the reagent by adjusting the concentration of the drug in the adhesive. can. In addition to the types of drugs mentioned above, nitroglycerin or motion sickness drugs may also be used as medicinal ingredients, if it is desired to include antibacterial agents in the adhesive, e.g. to treat acne. In some cases, such as applying adhesives to a patient's face for medical purposes or applying topical adhesives to the skin to treat infections locally, the adhesive may contain quaternary ammonium compounds, white 1, To treat athlete's foot, jock itch, and other localized fungal infections, suitable antimicrobial compounds are added to the adhesive.

As a self-supporting layer, this adhesive can also be used to secure prostheses to dancing mammals. Additionally, self-supporting layers from adhesives can be used to secure the ornament to the mammal's body.

In preparing the adhesives used in the present invention, radiation treatment is used to cause crosslinking of suitable rigid organic polymers. Irradiation treatments can be used to make films or coatings continuous in 5ite and, in addition, to cause global crosslinking (particularly when using gamma rays from cobalt-60). can. The use of radiation to crosslink synthetic organic polymers allows the use of high speed web processing techniques, resulting in the continuous production of extremely large quantities of adhesive coated substrates. A simple liquid process can be used to formulate the non-crosslinked composition onto a moving substrate web, which is then passed under a scanning electron beam.

When the carboxyl groups of the polymer react with the oxirane or aziridine groups of the crosslinking agent, resulting in ester bonds, and when significant amounts of water are present, preservation problems arise in chemically crosslinked polymers. Sometimes. In this case, the ester bond may not be hydrolytically stable for several weeks. Similarly, amide bonds formed by carboxyl groups on the polymer and amine groups on the crosslinker may not be hydrolytically stable. In contrast, carbon-carbon bonds formed between adjacent polymer molecules during irradiation are very stable.

Other advantages of using irradiation treatment are high efficiency, ease of handling, and removal of potentially toxic compounds. Irradiation is a clean method that is believed to leave no chemical toxins behind. Due to the ease of handling and the use of rapid processing equipment, the use of irradiation treatment is very cost-effective. Crosslinking can be done instantly without the need for lengthy processing cycles as required for epoxy effectiveness. Another advantage is that in some cases where chemical crosslinking is carried out, the crosslinked polymeric material must be dehydrated by air drying to convert the polymeric material from a flowable liquid state to a pressure sensitive adhesive. In contrast,
By applying a suitable amount of irradiation, such polymer compositions can be instantly converted into pressure-sensitive adhesives.

The theoretical irradiation dose rate can be calculated for the case of an electron beam using the following formula: where the energy loss is assumed to be similar to that of water, and d is the irradiation dose in megarads. , t is the time in minutes, A is the area of the scanning electron beam (ffl), I is the current (milliampere), and 1.1 is an experimental constant that depends on the irradiated material and the beam energy of 2 Mev. be. Scan width 152.4
Using a scanning electron beam with a scanning length of 5.08 ca in cm,
Using a current of 3-30 milliamps, the theoretical dose rate is calculated to be 2.5-25X109 rads. The material to be irradiated is passed under a scanning beam on a moving conveyor. In this case, the conveyor moves in the direction of the 5.08 cm scan axis so that the conveyor has a width of 152.4 cm.

Using a 100 milliamp source, the dose rate can be increased to 1 million square feet per day.

Because volatile organic solvents are not used in many cases in which the adhesives used in this invention are manufactured, solvent removal to obtain a "dry" adhesive does not require extensive contamination control or explosion protection equipment.

Under certain conditions it may be advantageous to add crosslinking promoters to solutions or dispersions of non-crosslinked polymers. Examples of accelerators include polymercaptans such as 2,
2-dimerkabutodiethyl ether, dipentaerythritol hexa(3-mercaptopropionate), ethylene-bis(3-mercaptopropionate), pentaerythritol pot tetra(3-mercaptopropionate), pentaerythritol φ tetrathioglycolate, polyethylene glycol dimercaptoacetate, polyethylene glycol di(3-mercaptopropionate), trimethylolethane tri(3-mercaptopropionate), trimethylolethane trithioglycolate, tri Methylolpropane tri(3
-mercaptopropionate), trimethylolpropane trithioglycolate, dithioethane, di- or trethiobrobane and 1,6-hexanediol.

In other embodiments of the invention, the adhesive is electrically conductive;
It is useful for attaching conductive members of electrodes to specific surfaces, such as mammalian tissue. The adhesive in this case is basically the same as the adhesive described above, except that the adhesive composition contains a conductivity enhancing substance. Conveniently, the conductivity enhancing substance is added as a solution or dispersion of a non-crosslinked polymer before the irradiation treatment step. Preferably, the conductivity enhancing substance is a non-toxic, ionizable organic or inorganic salt. The amount of conductivity enhancer used in adhesives depends on factors such as the type of conductivity-enhancing substance; substances with high conductivity require only a small amount, while substances with relatively low conductivity require a larger amount. It is. Examples of non-toxic, ionizable organic or inorganic salts include ammonium sulfamate, monoethanolamine acetate, jetanolamine acetate, sodium lactate, sodium citrate, sodium chloride, magnesium sulfate, and polyethylene glycol soluble salts). Examples include ammonium acetate, magnesium chloride and magnesium acetate). About 5% magnesium sulfate and about 7% ammonium acetate are suitable for use as adhesive conductivity enhancers. Mixtures of conductivity enhancers may also be used, for example a mixture of magnesium chloride and magnesium acetate can be utilized.

The conductive adhesive is particularly suitable for use as an electrode adhesive and is conveniently used to coat conductive substrates such as member 12 of FIG. Electrically conductive members are well known in the electrode art. therefore,
The discussion of conductive members here is limited to pointing out that the choice of the type of material used for the conductive member, together with the choice of its size, shape and thickness, depends on the final use of the electrode. Don't do it. Generally, the member 12 is about 0.38 m to about 3.18 m (approximately 1/1000
The thickness ranges from 5 to about 1/8 inch). As shown in FIG. 1, conductive adhesive 14 connects member 12 to surface 16
Functions to adhere to. Examples of electrodes that are applied to mammalian skin include transcutaneous nerve stimulation electrodes, electrosurgical return electrodes, and EKC monitoring electrodes.

Examples of the present invention are shown below, but it should be understood that these examples are merely illustrative. Percentages are by weight unless otherwise indicated.

Example I A solution containing 20% PVP, 25% PE0 and 55% water is prepared and a 1,5# coating of the solution is applied to one side of a white polyester fabric. The above PVP is G
PVPK-90 sold by AF Company, P
EG is Ca sold by Union Carbide.
rbovax 300, and the polyester fabric is similar to fibers commonly used to make white coats. A polyethylene protective film is applied to the coated cloth obtained as described above, and the sample is subjected to ionizing irradiation using a 2.5 Mev electron beam source at an irradiation dose of 3.5 Megarads. Repeat this operation to create multiple samples. The polyethylene membrane is removed from about half of the sample and the sample thus obtained is air dried at about 30% relative humidity and 20° C. for about 48 hours to form a "dry" sample.

The "wet" and "dry" samples were then subjected to a rotating ball adhesion test and were further tested for peel strength and lap shear.

The rotating ball adhesion test is performed as follows: A steel ball is placed in a ball with a length of 8.3 inches (21.1 cm) and a width of 0.
．． 21' to 53 inches (1,3C++) horizontal
Roll down the 30' inclined trough. Place the adhesive sample and determine the position of the adhesive when the ball rolling out of the end of the trough begins to adhere to the surface of the adhesive sample. The smaller this number is, the better the adhesive strength is.

The 180' peel strength of each sample is determined as follows: Two 1 inch (2,5 cm) wide specimens are placed on one side of a vertical steel plate 4 inches (10,2 cm) lengthwise.
), then fold back the remaining length of the sample and fix its free end. The steel plate is pulled vertically upward at a rate of 6 inches/minute (15.2 cm/minute) and the force with which the adhesive sample is peeled from the vertical steel plate surface is measured.

The 90" peel strength of each sample is determined as follows: A 1" (2,5c!n) wide sample is separated by 6" (15,2cm) in length from a vertical steel plate. One side is glued and the remaining length of the sample is glued to the top of a horizontal steel plate.

The vertical steel plate is moved vertically at a speed of 6 inches/minute (15.2 cm/minute) and the force required to peel the adhesive sample from the horizontal steel plate surface is measured. The samples used for peel strength testing varied in thickness for a given type of sample.

Also, those samples contained air bubbles.

Additionally, a solution of PVPSPEG and water is used to saturate the gauze strip to approximately 1 ml of adhesive. The saturated gauze thus obtained is placed between two polyethylene sheets and irradiated in the same manner as described above. Repeat this operation to prepare other samples and test for water vapor permeability and oxygen permeability. Before conducting this test, the top layer of polyethylene was removed from approximately half of the samples, and the particular samples thus obtained were air-dried for approximately 48 hours at a relative humidity of approximately 30% and 20°C. to obtain a “dry sample”.

Oxygen permeability is measured as:
cm> of adhesive sample is placed between two chambers, one side of the adhesive sample forming part of the wall of one chamber and the other side of the adhesive sample forming part of the wall of the other chamber. so that it forms. Oxygen flows from the cylinder regulator through the gas flow meter into the reservoir (which is connected to the nunometer). The oxygen pressure difference between the two chambers is set to 1 psi and the oxygen permeability is measured.

The results of the rolling ball adhesion test, peel strength test, lap shear test, and oxygen permeability are shown in Table 1. The water vapor permeability results are also shown in Table 2.

Examples 2-44 Adhesives, some of which are electrically conductive, are prepared using the compositions shown in Table 3. In each case, a solution or dispersion is prepared and a layer ranging in thickness from about 1 to 6 # is subjected to a 2.5 Mev electron beam irradiation source as indicated in the table. For compositions containing PVP and PEG, the layer thickness ranges from about 1 to 3 mm, and for other compositions from about 2 to 6 mm. The crosslinked material obtained in each case is an adhesive.

Also, some of the adhesives obtained by crosslinking have a
Air dry for approximately 48 hours at 20°C at % relative humidity. For these specific compositions, the corresponding dry adhesive formulas are shown in the table. In all cases, the corresponding "dry" substances are good adhesives.

Comparative Examples 1-5 Following the procedure of Examples 2-44 above, solutions or dispersions with compositions as shown in Table 4 were prepared and layers having thicknesses ranging from about 2 to 6 m were formed as shown in the table. It is subjected to electron beam irradiation at 2.5 Mev. In each case, the resulting crosslinked material is an adhesive. Each of these adhesives was air dried in the same manner as the adhesives of Examples 2-44. For those adhesives, the theoretical formulas for the corresponding "dry" adhesives are shown in the table. The "dry" material of Comparative Example 1 is a non-adhesive, brittle film, and the "dry" materials of the other four comparative examples exhibit non-adhesive, flexible films.

Example 45 A conductive adhesive is prepared using the following composition;
% Polyethylene glycol 300 (Carbowax3
00, manufactured by Union Carbide) 25% Magnesium acetate (reagent grade, J, T, manufactured by Baker) 7
% Methylparaben (manufactured by lnolex) 0
．． 037% propylparaben (manufactured by Inolex)
0.012%FD&CBIue #2 (11, Ko
hnstao+11) 0.0012% water
The remainder of the viscous liquid of the above composition is applied as a 1/15 inch (1.7#) thick layer to an electrosurgical return electrode pad as shown in FIG.

The impedance of the electrode is measured by configuring a circuit that allows current to flow across the electrode. To perform this measurement, first the entire surface of the electrode is fixed to a stainless steel plate. The stainless steel plate is then connected to the active electrode of a Val Ieylab Model SSE-3B electrosurgical generator, while the electrode under test is grounded to the generator's ground. Simpson (Siip
A Fluke type radio frequency ammeter was connected in series to the electrode/stainless steel plate.
A model 892OA RMS voltmeter is connected between the stainless steel plate and the electrode. A Model 5SE-3B generator is regulated to generate a 750,000 Hertz sine wave signal, and a Simpson type ammeter regulates the current to 1 amp. Read and memorize the voltage on the voltmeter. The results are shown in Table 5 as resistance per unit area.

The 11i0° peel strength test was carried out using a steel plate similar to the data in Table 1, and was also carried out using male and female skin as test objects. The procedure used is substantially the same as described for the 180° peel strength test in Table 1, except that the electrodes are peeled at a rate of 12 inches/second (60,5 cm/second) using a tensile testing apparatus. The points are different. Furthermore, when conducting tests using humans as test subjects, it is necessary to manually
) Pull the electrode pad using a 0-30 bond scale. In each experiment, an electrode pad is fixed to the human test subject's prick. The results are shown in Table 6.

Adhesives used in electrode pads are tested for irritation to human subjects, paying particular attention to discomfort during removal, hair, swelling, wound tension, and removal of epidermis. Fix the electrode pad to the target object 1
Remove within 0 minutes.

Perform similar tests equally. The obtained data is the seventh
shown in the table.

The electrical impedance of the electrodes was determined on a human test subject using a current of 1 ampere at 750,000 hertz. Several tests were conducted under the same conditions, and the data obtained are shown in Table 5 as average impedance per unit area.

The following tests were further conducted on the electrode pads.

That is, the pad is weighed and then heat-sealed to form a pouch laminated with aluminum foil. where the pouch has a density of 0.016 g/10 when one side thereof is brought to 37° C. at 90% relative humidity and the other side is air dried.
Have a moisture permeation rate less than 0 inch 2724 hours. The same operation is repeated and the resulting sealing pads are simultaneously placed in the Blue M oven. 2
Six pouches are removed at weekly intervals and left at room temperature for 18 hours. Thereafter, the pouch is opened, the pad is removed, the pad is weighed, and the electrical impedance and adhesion to the metal plate are determined. The test results are shown in Table 8.

In addition, vitri dish samples of irradiated adhesives were prepared to determine whether the irradiated adhesives supported bacterial or mold growth. On each of the four plates was a Serratia marcescens.
ens), Micrococcus O. lutea (Micr.

eoccus Iutea), E. coli (E. coli)
li) and Candida albicans (Candld
a albicans). The first of these inoculated plates was incubated at 2°C and the second at 25°C.
, the third one at 37°C, and the fourth one at 55°C, respectively. The fifth plate serves as a negative control and is left sealed at room temperature. The sixth plate is incubated for 1 week at 25°C and then an additional week at 37°C after being exposed to laboratory air for 15 minutes. No colony growth was observed on any of the six types of plates.

As a positive control, agar plates containing minimal nutrients are inoculated with the same bacteria and yeast and incubated at 37°C.

Colony growth is observed on this plate after 24 hours.

Comparative Example 6 A commercially available electrosurgical pad was used for comparison with the pad of Example 45. This pad (referred to as the "comparison pad") is a reticulated polyurethane sponge impregnated with a viscous gel, with a conventional adhesive along the border to secure the pad to a surface, such as the skin of a salivary mammal. Pressure adhesive is placed. The conductive member of the pad is a nickel alloy, and the viscous gel is 3% Carbo
po1934 (trade name), 3% sodium chloride, P
It consists of enough sodium hydroxide to adjust H to 7.0, and water.

The various tests performed on the electrode pad of Example 45 were performed, but without bacterial or yeast inoculation. In addition, in a test using the Blue M furnace,
Samples are placed in the furnace at the same time and removed from the furnace or processed at the same time. Tables 5 to 8 show the data obtained.

The present invention relates to dressings using a novel water-insoluble, hydrophilic, and elastic pressure-sensitive adhesive.

The adhesive is useful as a coating on a web-like supporting substrate or as a self-supporting layer. When supported by a web-like substrate, the adhesive may be used in bandages, wound or burn dressings, sanitary napkins, diapers, colostomy devices, bedsore pads, vibration or shock absorbers, sound absorbers, medicinal Useful as an adhesive on ingredient (medicinal) delivery media. Additionally, when used as a self-supporting layer, the adhesive is useful as a cosmetic facial mask or for securing a prosthesis or ornament to the body of a mammal. In one aspect of the invention, the adhesive is electrically conductive and is useful as an electrode adhesive. Examples of such electrodes include transcutaneous nerve stimulation electrodes, electrosurgical return electrodes,
and EKG monitor electrodes.

Table 1 Table 2 Water vapor permeability (STM3833) Wet sample AI A2 Ca Cl 2 initial weight 'fit Cg)
22.38 13.80 Initial weight of sample (f)
12.04 14.70Ca Hz absorbed in C12 OCg) 12.32 11.02 absorbed relative to initial sample weight 11.89 4.
63% sample increase of B20 ffi Cg>1.
43 0.88 water vapor transmission rate (g/100 inch2
) 353.94 316.87 Thickness 2 inches 0.12 0
．． 10 standard deviation 0.8
3 0.04 Dry sample BI B2 23.97 20.39 7.73 B, 40 14.30 15.40 28.98 29.84 2.24 ■, 91 410.92 442.43 0.07 0.06 0.01 0.01 Note 1 to Table 2: The temperature inside the sealed chamber is 100'F with a humidity of 90-95%.
It was maintained at ±1°.

Each sample is processed for 24 hours. The test ends when the desiccant reaches 100% absorption in 24 hours.

2: Average value of Δp] determined five times for each sample.

1 hoof-----

[Brief explanation of the drawing]

FIG. 1 is a plan view showing one example of the dressing of the present invention, and FIG.
The figure is a perspective view showing one example of the dressing of the present invention, and FIG. 3 is a perspective view showing one example of the dressing of the invention.

Claims (1)

[Scope of Claims] 1) A wound or burn dressing comprising a web-like substrate capable of supporting an adhesive and an adhesive covering this substrate, wherein the adhesive comprises at least one type of adhesive crosslinked by irradiation. A water-insoluble, hydrophilic, and elastic pressure-sensitive adhesive comprising a gel of a water-soluble synthetic organic polymer, a polyalkylene glycol plasticizer, and water, the crosslinked gel comprising the water and the plasticizer. formed from a solution or dispersion of the water-soluble synthetic organic polymer dissolved or dispersed therein, and wherein the cross-linked gel retains the plasticizer and the water within a three-dimensional matrix of the water-soluble synthetic organic polymer. Medical supplies characterized by the fact that they are 2) A dressing according to claim 1, wherein the plasticizer is present in a weight of about 0.2 to 4 times the weight of the polymer. 3) The dressing according to claim 1, wherein the polymer is polyvinylpyrrolidone. 4) The dressing according to claim 1, wherein the polymer is K-90 polyvinylpyrrolidone. 5) The polyalkylene glycol has a molecular weight of about 600 to
20,000 polyethylene glycol. 20,000 polyethylene glycol. 6) The dressing according to claim 1, wherein the polyalkylene glycol is polyethylene glycol having a molecular weight of about 300 or about 600. 7) A dressing according to claim 1, wherein said solution or dispersion contains about 12.5-22.5% by weight of said polymer. 8) A dressing according to claim 1, wherein said solution or dispersion contains about 20% by weight of said polymer. 9) The polymer is K-90 polyvinylpyrrolidone, and the plasticizer is polyethylene glycol having a molecular weight of about 300, and is present in an amount of about 0.7 to 1.5 times the weight of the polymer. The dressing according to claim 1. 10) The dressing according to claim 1, characterized in that the gel contains phosphate-buffered saline. 11) The dressing according to claim 1, characterized in that the gel contains a pharmaceutically active substance. 12) The dressing according to claim 1, which is in the form of a medical or athletic tape.