GB2434762A

GB2434762A - Absorbent elastomeric articles

Info

Publication number: GB2434762A
Application number: GB0602037A
Authority: GB
Inventors: Ian Philip Middleton; Janette Louise Rogers; Simon Thomas Pickard
Original assignee: Regent Medical Ltd
Current assignee: Regent Medical Ltd
Priority date: 2006-02-01
Filing date: 2006-02-01
Publication date: 2007-08-08
Also published as: GB0602037D0

Abstract

An elastomeric material comprises in order, a first elastomeric layer, a swellable, absorbant or hydrophilic layer, a protective layer and optionally a second elastomeric layer. The elastomeric layer(s) may comprises a natural rubber latex, the swellable layer may comprise superabsorbent (eg. lightly cross-linked polyacrylates) particles dispersed in a binder eg. hydroxyl substituted acrylates or methacrylates or cellulose ethers. The protective layer may be hydrophobic and is intended to prevent premature wetting of the absorbent layer during manufacture. The protective layer may comprise a polyurethane, a styrene-butadiene-styrene block copolymer or copolymers of vinylacetate/vinylalcohol with vinyl butyral or butyl maleate-co-isobomyl acrylate. The elastomeric material is particularly used for making surgical gloves, wherein the absorbent layer serves as sealing barrier if the glove is breached and by swelling, provides a visible indication of said breach. Gloves are produced by sequentially dipping the above layers onto a former, with the absorbent and protective layers being provided as non-aqueous solutions or dispersions.

Description

ABSORBENT ELASTOMERIC ARTICLES

The present invention relates to elastomeric articles such as gloves for surgical and examination procedures that have been constructed having an absorbent layer within the structure of such articles, and methods for their manufacture.

Protective articles, such as gloves for surgical or examination procedures, are conventionally manufactured from elastomeric materials in order to closely fit the contours of the body part to which they are applied, i.e. the hand, thereby maintaining manual dexterity and tactility. In addition the elastomeric materials generally used also provide a barrier effect, as the articles need to be resistant to body fluids and fluids/materials with which the gloves may come into contact. Such articles may be produced by dipping a suitably shaped former into a solution or suspension of the elastomeric material, withdrawing the former from the solution/suspension and evaporating the carrier liquid of the solution/suspension. More than one dipping process may be used to produce the final article.

A variety of elastomeric materials have been used for this purpose. For many years, the material of choice for such applications has been vulcanised natural rubber (NR) latex (the polymeric component of which is cis-polyisoprene) due to the excellent balance of softness, strength and elasticity exhibited by articles fabricated from it. A drawback of such elastomeric materials is that in providing a close fit to bodily contours it is often difficult for the wearer to discern if a breach of the material has occurred and the article must be changed to preserve the barrier function. Major breaches such as the glove completely tearing are obvious but minor breaches such as gloves being pierced by needles or jagged edges are far more difficult to discern. In surgical procedures double gloving (i.e. wearing two gloves on each hand) is often employed in an effort to avoid such an occurrence, but increasing use practice using implements such as fine suture needles often leads to undetected breaches of the glove's barrier protection. In addition the hydrophobic nature of the elastomeric materials used such as natural rubber effectively prevents the transport of moisture vapour (sweat) from the skin of the wearer thereby making the gloves increasingly uncomfortable to wear over an extended period and leading to diminished manual dexterity.

The close-fitting nature of elastomeric gloves also gives rise to donning difficulties, particularly when the wearer's hand is damp.

In order to aid donning of gloves, the application of a hydrophilic polymer layer to an elastorneric article such as a surgeon's glove has been suggested by Podell and Podell (US 4,499,154). This patent suggests the application of a hydrogel layer of poly(2-hydroxy ethyl methacrylate) (po1yHEMA) on the inner surface of a rubber surgeon's glove would act as a donning aid. Subsequent work (US 4,575476) demonstrated that a hydrogel terpolymer of HEMA, methacrylic acid (MAA) and 2-ethyl hexyl acrylate (EHA) could act as a donning aid if attached to the surface of an NR glove by crosslinking with the aid of a melamine formaldehyde resin. Neither of these polymers is sufficiently hydrophilic to function alone as an absorbent coating of the type envisaged for the present invention however.

A number of authors have suggested means by which an elastomeric article such as gloves may be produced with an indicating layer. Richardson and Richardson (U.S. patent 5,524,294) describe a tamper and damage indicating membrane comprised of two layers of materials with the second being translucent and of contrasting colour to the first. Upon a layer being breached in the presence of an aqueous liquid there is a change of colour in the area of the breach due to capillary action of the liquid between the two layers. The same authors (U.S. patent 5,817,365) extended this concept to a three-layered system with a separation layer between two latex layers. The separation material is described as being comprised of a gelatinous medium that may contain a coagulant (such as a calcium salt), a polymeric binder such as polyvinyl acetate and a nonfilm forming particulate material that is a water absorbent particulate mineral medium selected from a group consisting of calcium carbonate or diatomaceous earth. The indicating system is again due to capillary action of liquid between two layers of contrasting colours.

Shlenker et a!. (U.S. patents 5,165,953 and 5,549,924) describe a method of forming a polymer or latex membrane including a deactivating barrier and indicating layer. The membrane is comprised of a first latex layer that may be treated with a biocide, such as gentian violet, and a coagulant material that will act to prevent fusing of a second latex layer when applied to the first and cured. A method for making gloves having discrete inner and outer layers joined only in a cuff region is also described, the method of indicating breach again presumably due to capillary action.

While capillary action of liquid between two close-contacting layers is a viable method for indication of a breach in a glove, it is not always readily visually discernable to the wearer particularly in procedures using very fine needles.

Fuchs (U.S. patent 5,483,697) proposes a sealing solution between two latex layers with one example of a possible sealing solution being a swollen hydrogel. A structure of this type would impair manual dexterity, however. Brignol and Gidney (PCT/GB98/03019, now abandoned) suggested laminating a xerogel (a dehydrated hydrogel) layer between two latex layers. The method outlined for producing articles having this structure is to dip a former into aqueous rubber latex to form a first elastomer layer and, after drying, coating with a hydrophilic or hydrogel polymer dissolved or dispersed in an organic solvent. The article may then be dip coated with a second aqueous rubber latex layer and the former heated to drive off the solvent from the polymer solution or dispersion and the water from the second elastomer layer. However, this approach takes no account of any interaction between a hydrophilic or hydrogel polymer and water from the second coat of aqueous rubber latex and would lead to a water swollen gel layer trapped between two elastomer layers with the concomitant disadvantage of impaired manual dexterity as discussed above.

Thus, as described above, problems exist in the prior art. It is an object of the present invention to obviate or mitigate the disadvantages of the prior art. It would be highly desirable to provide a protective rubber article, such as a glove, which permits manual dexterity, provides an indication to the wearer when damaged, and provides an increased or additional protective barrier effect when damaged.

The present invention overcomes or alleviates the above-described problems. In particular, the present invention provides a glove which has an absorbent layer which, when a breach occurs, swells, indicating to the wearer that the breach has occurred and giving additional protection to the wearer's skin.

In a first aspect of the present invention there is provided a laminated elastomeric article having a first elastomeric layer; a protective layer; an absorbent layer disposed intermediate said first elastomeric layer and protective layer; and a second elastomeric layer overlying said protective layer, whereby the protective layer is disposed intermediate said absorbent layer and said second elastomeric layer.

The elastomeric layers are preferably impermeable to water and aqueous fluids.

Preferably, the absorbent layer is comprised of an absorbent hydrophilic material and a polymeric binder.

More preferably, the absorbent layer is preferably comprised a layer of particulate absorbent hydrophilic material embedded in said polymeric binder. The hydrophilic material may comprise a superabsorbent material.

The protective layer preferably comprises a hydrophobic polymeric layer.

The elastomeric article may be a glove, optionally for use in surgical or examination procedures. In the case where the article is a glove to be used for surgical or examination procedures, the overall laminate thickness is preferably 200 -400tm, more preferably 250 -300pm. The thickness of both the absorbent and protective layers (in combination) is preferably 20 -I 50tm, more preferably 40 -l20pm, most preferably 60 -l00jtm.

The thickness of the protective layer should preferably be sufficient to provide an aqueous-fluid impermeable layer on the surface of the absorbent layer. The thickness of the protective layer, on the other hand, should preferably be sufficiently thin not impede the manual dexterity of the article.

In use, as a glove on the hand of a wearer, the absorbent layer is preferably disposed closer to the hand of the wearer than the protective layer.

Each layer is preferably bonded to the or each adjacent layer.

In one embodiment, the laminated article further comprises a second absorbent layer disposed on one of the first or second elastomeric layers and forming an outer surface of said laminate.

The second absorbent layer may be comprised of a hydrophilic material disposed in a polymeric binder. The second absorbent layer is preferably comprised of a layer of particulate absorbent hydrophilic material embedded in said polymeric binder. The hydrophilic material may comprise a superabsorbent material.

In use, the second hydrophilic layer may be located adjacent to a wearer's skin, where it acts to absorb sweat thus allowing the article to be worn for extended periods without compromise to manual dexterity.

The construction and/or composition of the absorbent layer and the second absorbent layer may be the same.

The overall thicknesses of the glove and the absorbent and protective layers are as mentioned above, while the thickness of second absorbent hydrophilic layer is preferably 20 -I OOjim, more preferably 40 -80p.m, most preferably 50 -60jtm.

In an alternative embodiment, the second elastomeric layer is absent. In this embodiment, the first elastomeric layer is preferably worn against the skin, in use, with the protective coating being the outer surface of the laminated elastomeric article. A further elastomeric article, such as a latex glove, may be worn over the laminated elastomeric article, and will, in use contact and overlie the protective layer and thus provide an elastomeric outer surface to the laminated elastomeric article.

Thus, in another aspect of the present invention, there is provided a laminated elastomeric article having a first elastomeric layer; a protective layer; and an absorbent layer disposed intermediate said first elastomeric layer and protective layer.

In this embodiment, the protective layer is preferably comprised of a different material to the first elastomeric layer. Preferably the protective layer is comprised of a non-aqueous based hydrophobic polymeric material. Preferably the protective layer is deposited on the absorbent layer from a non-aqueous dispersion or suspension of a polymeric material. The protective layer may be comprised of a material which, during manufacture of the article, is applied in the absence of water. The protective layer may be non-elastomeric, and in particular, is preferably not comprised of latex.

Preferably in use the laminated elastomeric article is worn with the first elastomeric layer in proximity to a wearer's skin, and being disposed between the absorbent layer and the skin of the wearer. An additional elastomeric article may be worn exteriorly, in use, overlying the laminated elastomeric article according to the present invention. Thus, wherein the laminated elastomeric article is a glove, an additional elastomeric glove, such as an NR latex glove, may be worn over the laminated elastomeric glove, in contact with the protective layer (but not bonded thereto).

In this embodiment, the laminated elastomeric article may comprise, in use, a second elastomeric layer overlying said protective layer, said second elastomeric layer being separate from said protective layer.

The absorbent layers of the present invention may be constructed of an array of superabsorbent polymer particles embedded within a polymeric binder. The absorbent layers should be capable of rapidly absorbing relatively large amounts of aqueous fluid and swelling to indicate that absorption has occurred. Materials that would be highly suitable as superabsorbent polymer particles for this purpose are acrylic superabsorbent polymers (ASAP) that are based upon lightly crosslinked co-polymer particles of acrylic acid and sodium acrylate. Such materials are widely used in the manufacture of babies' diapers and feminine hygiene products.

A drawback to using materials of this type is that their rapid swell in aqueous fluids does not lend itself readily to fabrication processes in conjunction with aqueous based chemicals such as NR latex. Thus, if superabsorbent particles are added directly to NR latex they will rapidly absorb water causing the latex to destabilize and form a gel that cannot be applied to a former by dip coating.

It is thus another object of the invention to provide a method for manufacturing a laminate material comprising a layer of absorbent material, which overcomes or mitigates the problems of the prior art methods. In particular it is an object of the invention to provide a method by which hydrophilic absorbent layers containing superabsorbent ASAP particles may be applied to NR latex to produce articles having structures of the types described above.

In another aspect of the invention, there is provided a method for preparing a laminated elastomeric article having at least a first elastomeric layer; a protective layer; and an absorbent layer disposed intermediate said first elastomeric layer and said protective layer, the method comprising the steps of: applying an absorbent layer to the first elastomeric layer; and applying a protective layer to the absorbent layer.

Preferably the method further comprises the step of applying a second elastomeric to the protective layer.

The method may further comprises the step of drying the first elastomeric layer, prior to the step of applying said absorbent layer.

After the application of the absorbent layer, there preferably follows a step of drying the absorbent layer.

The step of applying the protective layer preferably follows the step of drying the absorbent layer.

The method may further comprise the step of drying the protective layer prior to the step of applying the second elastomeric layer.

While ASAP particles cannot be added directly to NR latex we have found that they may be applied directly to a layer of NR latex coated as a wet gel onto a former by applying them as a suspension in a solution of binder consisting of a suitable polymer or co-polymer or mixture of polymers and co-polymers. In a preferred embodiment, the binder is cross-linked.

The first latex elastomeric layer is preferably applied to a former, for example, in the shape of a hand.

In order to obtain good adhesion to the NR substrate it may be necessary for the solution of the polymeric binder to contain a plasticiser. The polymeric binder should preferably be soluble in an organic solvent that will suppress the swell of the ASAP particles, not produce a great degree of swelling of the rubber substrate and be relatively volatile in order to facilitate drying during the fabrication process. Examples of suitable solvents are lower homologues of alkyl alcohols such as methanol, ethanol, propan-1 -ol or propan-2-ol used either alone or in combination for instance as mixtures such as industrial methylated spirits (IMS).

The polymeric binders of the invention are preferably homopolymers or co-polymers that are soluble in an appropriate alcoholic solvent mixture and will not impede transport of aqueous fluid to the ASAP particles within the coated layer. Examples of suitable polymeric binders are hydrophilic polymers such as homopolymers and co-polymers of hydroxyl substituted acrylates and methacrylates e.g. 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA) and 2-hydroxypropyl methacrylate (HPMA), homopolymers and co-polymers of N-vinyl pyrrolidone (NVP), as well as hydroxyl substituted ethers of cellulose e.g. 2-hydroxyethyl cellulose, 2-hydroxypropyl cellulose and 2-hydroxypropyl methyl cellulose.

In cases where a hydroxylic polymer or co-polymer is used it may advantageous to induce a degree of crosslinking to the coating after application to the rubber surface. This may be conveniently be accomplished by inclusion of a crosslinking agent such as an appropriate melamine formaldehyde resin in the presence of an acid catalyst.

In certain circumstances it may be advantageous to use a polymeric binder based upon a mixture of two hydrophilic polymers e.g. a water-soluble polymer with a hydrophilic polymer that is insoluble in water, in conjunction with ASAP particles to obtain an absorbent layer having an appropriate balance of properties. A potential barrier to this approach is that certain hydrophilic polymers and co-polymers demonstrate incompatibility when they are dissolved to produce alcoholic solutions and mixed, resulting in precipitation of one of the polymeric components. If in these circumstances the water-soluble hydrophilic polymer is precipitated a homogeneous solution may be re-established by addition of water. If the amount of water added is less than 20% by weight of the overall solvent composition the suppression of aqueous swelling of ASAP particles is sufficient to enable the solution to be used to produce a suitable hydrophilic absorbent layer.

Plasticisers to be used in conjunction with polymeric binders for superabsorbent particles will in general be non-volatile polyhydric alcohols e.g. glycerol, 1,2 ethylene glycol, 1,2 propylene glycol or 1,3 propylene glycol, alternatively low molecular weight polyethylene glycol (PEG) materials such as PEG molecular weight 200 and PEG molecular weight 300 may be used.

In general the dispersions of ASAP particles from which the absorbent layers of the invention are fabricated are prepared by first dissolving the hydrophilic polymeric components in alcoholic solution. In certain cases this step is unnecessary as commercially available materials may be supplied already dissolved in a suitable alcohol.

The viscosity of the solution produced is largely dependent upon the chemical compositions, the molecular weights and concentrations of the polymer used. Polymer solutions having a viscosity greater than 500 centipoise (cP) have been found to produce dispersions than are resistant to sedimentation of the ASAP particles for 24-48hours.

Those solutions with a viscosity of lOOcP or less require stirring every 2-5 minutes to prevent sedimentation and preferably would be agitated continuously during application to the elastomer substrate.

The most preferred acrylic superabsorbent particles (ASAP) of the invention are lightly crosslinked co-polymers of acrylic acid and a monovalent metal ion salt of acrylic acid e.g. sodium acrylate, potassium acrylate, alternatively lightly crosslinked co-polymers of acrylamide, acrylic acid and a monovalent metal ion salt of acrylic acid may be used. The overall size of the ASAP particles to produce absorbent layer is preferred to lie in the range I-I 00jtrn, preferably 40-80tm, and more preferably 20-50jim. Particles of this type are capable of absorbing 300 gIg of de-ionized water and are available under the product name LiquiBlockTM 2G-l0 from Emerging Technologies Inc. of Greensboro, North Carolina, USA. Alternatively standard ASAP particles, commonly used in the production of babies diapers, generally having a particle size distribution of 150 -900 jim may be reduced in size by processing using a high speed rotor mill and separated to yield the appropriate particle size by sieving.

A wide range of polymers that have suitable water resistant properties (i.e. hydrophobicity) may be used as a protective coating for the absorbent layer. The choice of a polymer to act as a protective coating layer is influenced by a number of considerations as discussed below.

The solvent system used to apply the protective coating must not dissolve or disrupt the polymeric binder used to apply the absorbent layer. It is therefore advantageous in certain instances to apply the absorbent layer using a polymeric binder that may be crosslinked to avoid risk of dissolution or disruption by the application of the protective coating layer.

The polymer used as a protective coating layer must be compatible with both the polymeric binder used to apply the absorbent layer and the final NR latex layer to avoid delamination. In general this would exclude the use of rigid materials due to the difference in compliance between the layers leading to delamination. We have found that rigid materials may be used as protective coatings providing that they are plasticised to a sufficient degree to reduce the difference in compliance between the layers to a sufficient degree to avoid delamination. The choice of plasticiser is dependent upon the particular polymer chosen as a protecting layer, in certain cases non-volatile polyhydric alcohols of the type cited previously may be used but they are unsuitable for very hydrophobic materials where use of oils such as mineral oil or castor oil, or phthalate esters such as dioctyl phthalate are preferable.

The thickness of the protective coating layer is very important in that it must be sufficiently thick to coat all of the superabsorbent polymer particles completely as any portion of a particle left uncoated will be capable of imbibing and retaining water during the application of NR latex. The thickness of the protective coating layer should not be too thick however otherwise manual dexterity of a glove may be impaired.

Examples of materials that have been found suitable as a protective coating for the superabsorbent polymer particle layer are polyurethanes, styrene-butadiene-styrene block co-polymers, copolymers of polyvinyl acetate-c-butyl rnaleate-co-isobornmyl acrylate and copolymers of polyvinyl acetate-co-vinyl alcohol-co-vinyl butyral plasticised with mineral oil. This list is by no means exhaustive and is provided only to illustrate some examples of the range of polymers that may be used.

The invention will now be described further with reference to the drawings, in which: Figure 1 is a cross-sectional representation of an embodiment of a laminate according to the present invention; and Figure 2 is a cross-sectional representation of an embodiment of a laminate according to the present invention comprising an additional absorbent layer.

The structure comprises a first layer I and a final layer 8 formed from an aqueous rubber latex. Surfaces 2 and 9 thus form the inner and outer surfaces of the final article.

The absorbent hydrophilic layer 4 is applied to surface 3 of the first rubber latex layer I and after drying is protected from ingression of water by application of a coating of a hydrophobic polymer layer 6 onto surface 5. Upon drying of the protective coating 6 the final layer 8 of an aqueous rubber latex is applied to surface 7 and dried to yield the overall laminate structure.

Should a breach to the article thus constructed occur any aqueous based fluid would be absorbed by layer 4 thereby maintaining the article's barrier function. In addition the swell of the absorbent layer would serve to indicate that the breach had occurred and that the article should be changed.

Figure 2 shows an embodiment of the invention in which an additional absorbent layer is provided Ofl an outer surface of the article. Thus an article produced as described above would be modified by application of a second absorbent hydrophilic layer 10 to surface 9 of the second rubber latex layer 8 to produce a moisture absorbing surface 11.

When the article is intended as a glove, the moisture absorbing surface 11 will be positioned as the inner glove surface next to the wearer's skin.

The invention will now be described further with reference to the following non-

limiting examples.

Example I.

A ceramic plate was washed with detergent, rinsed with warm water and dried at 70-80 C for 20 minutes. The plate was then dipped into a warm (70 C) aqueous coagulant solution comprised of calcium nitrate (100 g/litre), calcium carbonate (35 g!litre) and sodium dodecylsulphate (0.04 g/litre) at a speed of 4.9 mm/second allowed to dwell for 3 seconds and withdrawn at the same speed before being dried at 70-80 C for 1-2 minutes.

The plate was then dipped into natural rubber (NR) latex that had previously been compounded with sulphur and other vulcanization agents at a speed of 4.9 mm/second allowed to dwell for 10 seconds and withdrawn at the same speed before being dried at 110 C for 1-2 minutes. The plate was then dipped into a dispersion of superabsorbent polymer particles (Liquiblock 2G-1 0, cx Emerging Technologies Inc. of Greensboro, North Carolina, USA) prepared by suspending 300 g / litre of the particles in a 4% w/w alcoholic solution of a terpolymer of 2-hydroxy ethyl methacrylate (HEMA), methacrylic acid (MAA) and 2-ethyl hexyl acrylate (EHA) that also contained 0.4% w/w of a melamine formaldehyde crosslinking agent (Cymel 370) and 0.02% of a catalyst (Cycat 4040). The plate was dipped into the dispersion at a speed of 4.9 mm / second allowed to dwell for 3 seconds and withdrawn at the same speed while the dispersion was continuously stirred, before crosslinking the rubber and the superabsorbent polymer coating at 110 C for 30 minutes. The coated rubber film was allowed to cool before being stripped from the plate with the aid of talcum powder to prevent blocking of the rubber surface. The superabsorbent particle layer was found to be well adhered to the rubber substrate and when tested by applying a droplet of de-ionised water to the surface from a fine syringe needle, the liquid droplet was converted to a gel within 10 seconds. When the test was repeated using 0.9% saline the time for gelation was longer but the liquid droplet was converted to a gel within 30 seconds.

Example 2

A ceramic plate was prepared and dip coated using identical conditions to those described in example 1. After crosslinking the rubber and the superabsorbent polymer coating the film was dipped into NR latex at a speed of 4.9 mrnlsecond allowed to dwell for 5 seconds and withdrawn at the same speed and then dried at 110 C for 30 minutes.

The coated rubber film was allowed to cool before being stripped from the plate with the aid of talcum powder. When inspected it was found that the superabsorbent particle layer had swollen by taking up and retaining water from the application of the second NR latex coat despite drying at high temperature.

Example 3

A ceramic plate was prepared and dip coated using identical conditions to those described in example 1. After crosslinking the rubber and the superabsorbent polymer coating the film was allowed to cool for 10-20 minutes at ambient temperature before being dipped into a solution of a 15 % w/w polycarbonate urethane (Carbothane 75A ex Thermedics Inc., Wobum Massachusetts, USA) in dimethylacetamide at a speed of 7.3 mm / second and immediately withdrawn. The polycarbonate urethane layer was dried at 110 C for 20 minutes before being dipped into NR latex at a speed of 4.9 mmlsecond allowed to dwell for 5 seconds and withdrawn at the same speedand then dried at 110 C for 30 minutes. The coated rubber film was allowed to cool before being stripped from the plate with the aid of talcum powder. It was observed that no water from the second NR latex coat had penetrated into the superabsorbent particle layer.

Example 4

A ceramic plate was prepared and dip coated with NR latex using identical conditions to those described in example 1. The plate was then dipped into a dispersion of superabsorbent polymer particles (Liquiblock 2G-10, cx Emerging Technologies Inc. of Greensboro, North Carolina, USA) prepared by suspending 450 g / litre of the particles in a 13% w/w methanolic solution of polyvinylpyrrolidone (Plasdone K90 ex International Specialty Products, Tadworth, Surrey, UK) containing 160 g/ litre of glycerol as a plasticiser. The plate was dipped into the dispersion at a speed of 4.9 mm / second allowed to dwell for 3 seconds and withdrawn at the same speed while the dispersion was continuously stirred, before crosslinking the rubber and the superabsorbent polymer coating at 110 C for 30 minutes. The coated rubber film was allowed to cool for 10-20 minutes at ambient temperature before being dipped into a solution of a 25 % w/w solution of a styrene-butadiene-styrene block copolyrner (Kraton Dli 61 cx Kraton Polymers, Tattenhall, Cheshire, UK.) in toluene. The styrene-butadiene-styrene block copolymer layer was dried at 60 C for 10 minutes followed by 110 C for 10 minutes before being dipped into NR latex at a speed of 4.9 mm/second allowed to dwell for 5 seconds and withdrawn at the same speed and then dried at 110 C for 30 minutes. The coated rubber film was allowed to cool before being stripped from the plate with the aid of talcum powder. It was observed that no water from the second NR latex coat had penetrated into the superabsorbent particle layer.

It will be appreciated that the invention described above can be modified within the scope of the appended claims.

Claims

Claims 1. A laminated elastomeric article having a first elastomeric

layer; a protective layer; an absorbent layer disposed intermediate said first elastomeric layer and protective layer, and a second elastomeric layer overlying said protective layer, whereby the protective layer is disposed intermediate said absorbent layer and said second elastomeric layer.

2. A laminated elastomeric article having a first elastomeric layer; a protective layer; and an absorbent layer disposed intermediate said first elastomeric layer and protective layer.

3. A laminated elastomeric article according to claim 2, wherein, in use, the first elastomeric layer is worn against the skin, and wherein the protective coating forms the outer surface of the laminated elastomeric article.

4. A laminated elastomeric article according to claim 2 or 3, further comprising an additional elastomeric article overlying the protective layer.

5. A laminated elastomeric article according to claim 4, wherein the laminated elastomeric article is a glove, and the additional elastomeric article is a glove.

6. A laminated elastomeric article according to any preceding claim, wherein the protective layer comprises a polymeric material, and the polymeric material is deposited on the absorbent layer from a non-aqueous dispersion or suspension of the polymeric material.

7. An elastomeric article according to any preceding claim, further comprising a second absorbent layer disposed on the opposite side of the first elastomeric layer to the absorbent layer.

8. An elastomeric article according any preceding claim, wherein the or each absorbent layer is comprised of an absorbent hydrophilic material and a polymeric binder.

9. An elastomeric article according to any preceding claim, wherein the or each absorbent layer is comprised of a layer of a particulate absorbent hydrophilic material embedded in a polymeric binder.

10. An elastomeric article according to claim 8 or 9, wherein the absorbent hydrophilic material comprises a superabsorbent material.

11. An elastomeric article according to any of claims 8 or 9, wherein the polymeric binder is a homopolymer or co-polymer of a hydroxyl substituted acrylate or methacrylate; a homopolymer and co-polymer of N-vinyl pyrrolidone (NVP); or a hydroxyl substituted ether of cellulose.

12. An elastomeric article according to claim 8 or 9, wherein the polymeric binder is 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxyethyl cellulose, 2-hydroxypropyl cellulose and 2-hydroxypropyl methyl cellulose.

13. An elastomeric article according to any of claims 8 to 12, wherein the polymeric binder is based upon a mixture of two hydrophilic polymers.

14. An elastomeric article according to any of claims 8 to 13, wherein the polymeric binder is used in conjunction with a plasticizer.

15. An elastomeric article according to any of claims 8 to 14, wherein the absorbent hydrophilic material is comprised of an acrylic superabsorbent polymer (A SAP) based on a copolymer of acrylic acid and a monovalent metal ion salt of acrylic acid, or a co-polymer of acrylamide, acrylic acid and a monovalent metal ion salt of acrylic acid.

16. An elastomeric article according to any of claims 8 to 15, wherein the absorbent hydrophilic material is comprised of an acrylic superabsorbent polymer (ASAP) based on co-polymer particles of acrylic acid and sodium acrylate.

17. An elastomeric article according to any of any preceding claim, wherein the or each absorbent layer is comprised of acrylic superabsorbent polymer particles having a mean diameter in the range of I to 1 OOj.im.

18. An elastomeric article according to any preceding claim, wherein the or each absorbent layer is comprised of acrylic superabsorbent polymer particles having a mean diameter in the range of 40 to 8Ojtm.

19. An elastomeric article according to any preceding claim, wherein the or each absorbent layer is comprised of acrylic superabsorbent polymer particles having a mean diameter in the range of 20 to 50tm.

20. An elastomeric article according any preceding claim, wherein the protective layer is comprised of a hydrophobic polymeric material.

21. An elastomeric article according to any preceding claim, wherein the protective layer is a polyurethane, a styrene-butadiene-styrene block co-polymer, a copolymer of polyvinyl acetate-c-butyl maleate-co-isobormnyl acrylate, or a copolymer of polyvinyl acetate-co-vinyl alcohol-co-vinyl butyral plasticised with mineral oil.

22. An elastomeric article according to any preceding claim, when dependent on claim 7, wherein the thickness of the second absorbent layer in the range of 20 to 1 00gm.

23. An elastomeric article according to any preceding claim, when dependent on claim 7, wherein the thickness of the second absorbent layer in the range of 20 to l00jim.

24. An elastomeric article according to any preceding claim, when dependent on claim 7, wherein the thickness of the second absorbent layer in the range of 40 to 80tm.

25. An elastomeric article according to any preceding claim, when dependent on claim 7, wherein the thickness of the second absorbent layer in the range of 50 to 60j.im.

26. An elastomeric article according to any preceding claim, wherein the, or each, elastomeric layer is comprised of latex, preferably natural rubber latex.

27. An elastomeric article according to any preceding claim, wherein the laminate thickness is in the range of 200 to 400tm.

28. An elastomeric article according to any preceding claim, wherein the laminate thickness is in the range of 250 to 300tm.

29. An elastomeric article according to any preceding claim, wherein the thickness of the absorbent and protective layers in combination is in the range of 20 to 1 5Ojtm.

30. An elastomeric article according to any preceding claim, wherein the thickness of the absorbent and protective layers in combination is in the range of 40 to 1 20im.

31. An elastomeric article according to any preceding claim, wherein the thickness of the absorbent and protective layers in combination is in the range of 60 to I OOjtm.

32. An elastomeric article according to any preceding claim, in the form of a glove.

33. A method for preparing a laminated elastomeric article having at least a first elastomeric layer; a protective layer, and an absorbent layer disposed intermediate said first elastomeric layer and the protective layer, the method comprising the steps of: applying an absorbent layer to the first elastomeric layer; and applying a protective layer to the absorbent layer.

34. A method according to claim 33, further comprising the step of applying an elastomeric material to said protective layer to form a second elastomeric layer.

35. A method according to claim 33 or 34, wherein the, or each, elastomeric layer is comprised of latex, preferably natural rubber latex.

36. A method according to claim 33, 34 or 35, wherein the protective layer is comprised of a polymeric material, and the step of applying the protective layer comprises depositing a layer of the protective material on the absorbent layer, from a non-aqueous solution or dispersion of the polymeric material.

37. A method according to claim 36, wherein the polymeric material is a polyurethane, a styrene-butadiene-styrene block co-polymer, a copolymer of polyvinyl acetate-c-butyl maleate-co-isobornmyl acrylate, or a copolymer of polyvinyl acetate-co-vinyl alcohol-co-vinyl butyral plasticised with mineral oil.

38. A method according to claim 36 or 37, wherein the polymeric material is polycarbonate urethane or Kraton Dl 161.

39. A method according to claim 36, 37 or 38, wherein the polymeric material is dissolved in an organic solvent.

40. A method according to claim 39, wherein the organic solvent is toluene or dimethylacetamide.

41. A method according to any of claims 33 to 40, further comprising the step of drying the first elastomeric layer, prior to the step of applying the absorbent layer.

42. A method according to any of claims 34 to 41, further comprising the step of, after the application of the absorbent layer, drying the absorbent layer.

43. A method according to claim 42, wherein the step of applying the protective layer follows the step of drying the absorbent layer.

44. A method according to any of claims 33 to 43, further comprising the step of drying the protective layer prior to the step of applying the second elastomeric layer.

45. A method according to any of claims 33 to 44, wherein the absorbent layer is comprised of a particulate absorbent material disposed in a polymeric binder.

46. A method according to claim 45, wherein the binder is dissolved in a lower alkyl alcohol, such as methanol, ethanol, propan-1 -ol or propan-2-ol, used either alone or in combination.

47. A method according to claim 45 or 46, further comprising the step of preparing a dispersion of said absorbent particles by dissolving hydrophilic polymeric components in alcoholic solution.

48. A method according to claim 47, wherein the dispersion of said absorbent particles has a viscosity greater than 500 centipoise (cP).

49. A method according to any of claims 33 to 48, wherein the absorbent layer comprises superabsorbent particles, the first elastomeric layer is comprised of natural rubber latex, and wherein the absorbent layer is applied directly to the first elastomeric layer of natural latex coated as a wet gel onto a former by applying the particles as a suspension in a solution of a binder.

Use of an elastomeric article according to any of claims 1 to 31 as a glove.

51. An elastomeric article substantially as herein described, with reference to and as shown in the drawings.

52. A glove, substantially as herein described, with reference to and as shown in the drawings.