WO1996008353A1 - Articles elastomeres - Google Patents

Articles elastomeres Download PDF

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Publication number
WO1996008353A1
WO1996008353A1 PCT/US1995/011765 US9511765W WO9608353A1 WO 1996008353 A1 WO1996008353 A1 WO 1996008353A1 US 9511765 W US9511765 W US 9511765W WO 9608353 A1 WO9608353 A1 WO 9608353A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
article
thin walled
emulsion
carbon atoms
Prior art date
Application number
PCT/US1995/011765
Other languages
English (en)
Inventor
Andrew Patrick Jackson
Original Assignee
Ansell Perry Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ansell Perry Inc. filed Critical Ansell Perry Inc.
Publication of WO1996008353A1 publication Critical patent/WO1996008353A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen

Definitions

  • This invention relates to elastomeric thin walled articles and methods for their preparation.
  • Elastomeric thin walled articles such as gloves for surgical use are generally manufactured from natural rubber, usually by dipping a glove former into a vessel containing natural rubber latex.
  • a glove former into a vessel containing natural rubber latex.
  • problems have been encountered with natural rubber surgical gloves since small quantities of proteins may leach from the glove into an open surgical site and in some instances cause an allergenic reaction to the patient.
  • European Patent application No.0413467 discloses polyurethane condoms which are manufactured by dipping a suitably shaped former into an organic solvent solution of a polyurethane.
  • Such processes have a major disadvantage in that undesirable solvents must be used thus giving rise to increased costs and problems with waste products.
  • thin walled polyurethane articles having a tensile strength of from 10 to 24 MPa.
  • the improved tensile set properties may be obtained by including a plasticiser in the polyurethane emulsion.
  • a plasticiser in particular we have found that specific plasticisers are advantageous.
  • Particularly preferred plasticisers are those disclosed in US Patent No.3779975.
  • the polyurethane comprises a plasticiser with a diaryl sulphone-ester having the general formula
  • a method of manufacturing a thin walled polyurethane article which comprises dipping a shaped former into an aqueous polyurethane emulsion comprising a plasticiser as hereinbefore described.
  • the amount of plasticiser present in the polyurethane emulsion may be from 0.1 to 40% w/w, preferably from 0.1 to 20% w/w and especially from 0.1 to 10% w/w, eg. 5% w/w plasticiser.
  • Plasticisers of particular value are diaryl sulphone mono- and diesters in which the aforesaid R and R' groups are straight or branched chain alkyl or alkenyl radicals containing from 7 to 22 carbon atoms, especially mono- and diesters derived from long chain aliphatic monocarboxylic acids such as lauric, palmitic, stearic, oleic and linoleic, saturated tertiary monocarboxylic acids, and other aliphatic monocarboxylic acids containing particularly 9 to 18 carbon atoms.
  • plasticisers mentioned herein may be manufactured using methods in US Patent No.3779975.
  • a method of manufacturing a thin walled polyurethane article which comprises dipping a shaped former into an aqueous polyurethane emulsion as hereinbefore described which emulsion comprises a substantial number of particles with a mean particle size of greater than 0.3 ⁇ m and a plasticiser.
  • mean particle size is meant the mean diameter for generally spherical particles.
  • the mean particle size of polyurethane emulsions can be measured using conventional methods known QSL se_, such as electron microscopy or a conventional particle size analyser, eg. a Malvern Analyser.
  • the mean particle size may be from 0.31 ⁇ m to 2.5 ⁇ m, preferably from O. ⁇ m to 2.0 ⁇ m, more preferably from 0.5 ⁇ m to 1.5 ⁇ m, eg. 1.0 ⁇ m.
  • a substantial number of the particles in the polyurethane emulsion may have a particle size of greater than 0.3 ⁇ m.
  • substantial number we mean at least 50% w/w, preferably at least 70% w/w and more preferably at least 80% w/w and especially at least 90% w/w of the particles have a particle size of greater than 0.3 ⁇ m when measured using electron microscopy. Similarly a substantial number of particles fall within the limits of the preferred mean particle sizes hereinbefore defined.
  • surfactant in the polyurethane emulsion as hereinbefore described increases the stability of a large particle size polyurethane emulsion and provides advantageous film forming properties.
  • surfactant in the manufacture of thin walled articles it may be advantageous to have a surfactant present.
  • the polyurethane emulsion as hereinbefore described comprises from 0.1 to 10% w/w of surfactant, preferably from 2 to 8% w/w and especially from 4 to 6% w/w, eg. 5% w/w.
  • the amount of surfactant may vary according to the type of surfactant used, the nature of the polyurethane, the particle size of the polyurethane, the solids content of the emulsion, etc. Generally however, the amount of surfactant present should be at least sufficient to exceed the critical micelle concentration in the emulsion. More particularly, it is preferred to use an amount of surfactant in the emulsion so that the surface tension of the emulsion, measured using conventional methods known p_e ⁇ ⁇ e, approaches that of natural rubber latex.
  • the emulsion possesses a surface tension of from 20 to 50 dynes cm ⁇ 1 , preferably from 25 to 45 dynes cm -' ' , more preferably from 30 to 40 dynes cm"1 , eg. 35 dynes cm -1 .
  • Any conventional surfactant may be used including non-ionic surfactants, ionic surfactants, eg. anionic surfactants, or a mixture of two or more ionic and non-ionic surfactants.
  • ionic surfactants eg. anionic surfactants
  • anionic surfactants are preferred.
  • suitable anionic surfactants include carboxylate surfactants.
  • Carboxylate surfactants are typically derived from C10 to C20 straight chain fatty acids which may optionally be saturated or unsaturated.
  • Conventionally known salts of carboxylate surfactants may be used, such salts include ammonium or alkyl ammonium salts, eg. triethylamine or morpholine salts; or alkali metal salts, eg. sodium or potassium salts.
  • salts of other acids may be used including oleic, ncinoleic and rosin acids or the n- alkyl sarcosides.
  • the invention is not limited to the surfactants hereinbefore described and may also include mixtures of two or more surfactants.
  • Non-ionic surfactants are particularly preferred and examples of suitable non-ionic surfactants include those described in "Surfactant and Interfacial Phenomens" Miltan J Rosen, (John Wiley & Sons Inc (1978)).
  • suitable non-ionic surfactants include those described in "Surfactant and Interfacial Phenomens" Miltan J Rosen, (John Wiley & Sons Inc (1978)).
  • non-ionic surfactants which may be mentioned are, polyoxyethylene alkylphenols; alkylphenol ethoxylates, examples of alkylphenols are p-nonylphenol, p-octylphenol or p-dodecylphenol; polyoxyethylenated straight chain alcohols; alcohol ethoxylates (the alcohols are typically derived from coconut or tallow oils or are synthetic long carbon chain alcohols); polyoxyethylenated polyoxypropylene glycols (derived from ethylene oxide and propylene oxide);
  • glycerol and polyglyceryl esters of natural fatty acids propylene glycol, sorbitol and polyoxyethylenated sorbitol esters; polyoxyethylene glycol esters and polyoxyethylenated fatty acids; alkanolamine condensates; alkanoiamides, eg. alkanolamine/fatty acid condensates; and tertiary acetylenic glycols.
  • a thin walled polyurethane article comprising from 0.1 to 40% w/w of a plasticiser as hereinbefore described and from 0.1 to 10% w/w of surfactant.
  • the thin walled article comprises from 2 to 10% w/w surfactant more preferably from 4 to 10% w/w and most preferably from 6 to 8% w/w.
  • the concentration of the polyurethane in the aqueous emulsion ie. the solids content, may be from 10 to 60% w/w, preferably 20 to 60% w/w, preferably 40 to 60% w/w, and especially 45 to 55% w/w, eg. 52 to 53% w/w.
  • the molecular weight of the polyurethane in the emulsion may vary, but preferably the weight average molecular weight (M w ) is from 50,000 to 1 ,000,000, more preferably from 50,000 to 800,000.
  • the number average molecular weight (M n ) may be from 4000 to 1500, preferably from 5000 to 12000.
  • Emulsions are especially preferred wherein the molecular weight distribution tends to be binodal, that is, the emulsion comprises a relatively high molecular weight component and a relatively low molecular weight component.
  • the relatively high molecular weight component may have a weight average molecular weight in the region of from 50,000 to 150,000, preferably from 75,000 to 125,000, eg. 100,000
  • the relatively low molecular weight component may have a weight average in the region of from 1000 to 2000, preferably from 1200 to 1800, eg. 1600.
  • the relative ratio of the high molecular component to the low molecular weight component may be from 4:1 to 3:2, preferably 3:1.
  • a thin walled polyurethane article comprising from 0.1 to 40% w/w of a plasticiser as hereinbefore described wherein the polyurethane has a weight average molecular weight of from 50,000 to 1 ,000,000.
  • the polyurethane emulsion may comprise a salt forming moiety to confer dispersibility, such as an amine, eg. diethanolamine or morpholine, or a cationic species, eg. sodium, potassium, ammonium, etc.
  • a salt forming moiety to confer dispersibility such as an amine, eg. diethanolamine or morpholine, or a cationic species, eg. sodium, potassium, ammonium, etc.
  • Preferred amines include tertiary amines and especially tertiary alkyl amines, such as triethylamine.
  • polyurethanes may be used in the manufacture of the articles of the invention.
  • preferred polyurethanes are anionic polyurethanes and especially those prepared from polyethers or polyesters.
  • Aromatic polyesters may be used but aliphatic polyesters are preferred.
  • aromatic diisocyanates may be used, aliphatic diisocyanates are preferred. It is especially preferred to use diisocyanates which can render flexibility to the polyurethane, such as cyclohexane diisocyanates and alkylcyclohexane diisocyanates.
  • Preferred polyurethanes are those sold under the name UCECOAT (Trade Mark), such as UCECOAT XE102.
  • the most preferred polyurethanes are those sold under the name WITCOBOND (Trade Mark) available from Baxenden in the UK. WITCOBOND 740 is especially preferred.
  • a thin walled article made from a plasticiser as hereinbefore described and a polyurethane selected from WITCOBOND and UCECOAT, especially WITCOBOND, eg. WITCOBOND 740.
  • the method according to the invention may advantageously include a coagulant dipping step in the process.
  • a method of manufacturing a thin walled polyurethane article which comprises first dipping a suitably shaped former into a coagulant solution, optionally drying the coagulant coated former, followed by dipping the coagulant coated former into a polyurethane emulsion comprising a plasticiser as hereinbefore described.
  • Preferred coagulants are ionic coagulants, eg. mono, di- and tri- valent cations.
  • monovalent cationic coagulants include quarternary ammonium salts such as cyclohexylamine salts, eg. cyclohexylamine acetate.
  • Divalent cationic coagulants are preferred, such as alkaline earth metal salts, eg. calcium salts, or transition metal salts, eg. zinc salts. The nitrates of these salts are preferred and thus the most preferred coagulant is calcium nitrate.
  • heat sensitising agents may also be used.
  • heat sensitising agents such as polyether siloxanes may be used, such agents are sold as coagulant WS by Bayer.
  • Heat sensitivity coagulants are generally mixed with the polyurethane emulsion.
  • the amount of coagulant present in the coagulant solution may be from 5 to 60% w/w solution, preferably from 5 to 30% w/w, preferably from 5 to 20% w/w, more preferably 8 to 12% w/w and especially 10% w/w.
  • the method according to the invention may also include a curing step.
  • a curing step may also include a curing step.
  • the formed article may be cured at from 60° to 150°C, preferably from 60° to 120°C and more preferably from 70° to 100°C, eg. 90°C.
  • Curing times may vary according to, inter alia, the thickness of the formed article. Curing times of from 5 to 60 minutes are appropriate.
  • the method according to the invention may include a leaching step. Leaching may be carried out before or after curing the formed article, or leaching may be carried out both before and after curing.
  • the leaching process is intended to, inter alia, remove residual coagulant and/or surfactant. It may be a characteristic of the thin walled polyurethane articles according to the invention that residual coagulant and/or surfactant may remain in the polyurethane.
  • a thin walled polyurethane article wherein the polyurethane comprises a plasticiser as hereinbefore described and a coagulant residue of from 2 to 15mg/g (of polyurethane) preferably from 2 to 12mg/g, more preferably from 3 to 10mg/g.
  • the residual coagulant may be detectable in the form of calcium ions.
  • conventional techniques known ⁇ rse may be used in, eg. calcium ion analysis. Such methods include, inter alia, atomic absorption spectrometry.
  • Additives may be included in the coagulant solution or the emulsion to improve the release properties of the polyurethane article allowing the cured article to be more easily removed from the former.
  • the stripping of the article from the former may be improved by the inclusion of a detackifier.
  • Any conventional detackifiers may be used including powders such as chalk, starch, eg. maize starch or corn starch, slays, lycopodium powders, talc or ground whiting.
  • liquid detackifiers conventionally used with natural rubbers may be used, these include silicone emulsions, silicone oils or polypropylene glycols.
  • the thin walled articles manufactured by the process of the invention may also be detackified by surface treatment, such as chlorination or bromination or surface coating.
  • the powdered detackifiers may be applied in the coagulant or after the glove has been cured, but the preferred detackifiers are carbonates, such as alkaline earth metal carbonates, eg. calcium carbonate.
  • the level of detackifier present in the glove may vary, but preferred levels are from 0.1 to 10% w/w, preferably from 2.5 to 7.5% w/w, most preferably 5% w/w.
  • the thickness of the flexible thin walled polyurethane articles may be from 0.03 to 1.0mm, preferably from 0.05 to 0.8mm and especially from 0.05 to 0.5mm.
  • Such articles are advantageous in that the tensile strength or the force required to break the polyurethane remains sufficient to give the article utility.
  • a flexible thin walled polyurethane article having a tensile strength of from 2 MPa to 60 MPa.
  • Such tensile strength is preferably from 5 to 40 MPa, more preferably from 10 to 40 MPa and especially from 15 to 40 MPa, eg. 24 to 40 MPa.
  • the articles according to the invention have an advantageous value for elongation at break.
  • a flexible article made from polyurethane having an elongation at break of greater than 450%, eg. 500 to 600%, eg. 550%.
  • the thin walled articles of the invention include gloves, eg. gloves for surgical use, condoms, sleeves, catheters, boots, bladders, balloons, teats, enema tips and other tubular articles.
  • a 4mm wide dumbbell cutter was used to cut a sample of film. Reflective markers stuck to the parallel part of the test piece identified a 25mm length.
  • a tensile test was carried out with a crosshead speed of 500mm min ⁇ 1 using a Zwick 1435 tensile testing machine. An extensometer measured the true strains during the test by following the reflective markers. The stresses at 100, 300 and 500% strain were recorded along with the stress and strain at break.
  • Percentage Set is defined as the permanent deformation following the application and removal of strain.
  • a 4mm wide dumbbell cutter was used to cut a sample of film, and reflective markers were stuck on about 25mm apart. The sample was stretched to 300%, and immediately relaxed. The second gauge length between the reflective markers was measured under a very small load. Percentage set is defined as:
  • % set (2nd gauge length - 1st gauge length ⁇ * 100% (1st gauge length)
  • the samples were analysed using gel permeation chromatography (GPC) and a refractive index detector.
  • GPC gel permeation chromatography
  • the calcium content of polyurethane films was determined after ashing the samples of the polyurethane film, taking up the ash in water (25ml) and then diluting further as appropriate. Calcium standards at 1.0, 2.0, 3.0 and 4.0 ⁇ g/ml in water were used to quantify the calcium present.
  • Example 5 The calcium content of polyurethane films was determined after ashing the samples of the polyurethane film, taking up the ash in water (25ml) and then diluting further as appropriate. Calcium standards at 1.0, 2.0, 3.0 and 4.0 ⁇ g/ml in water were used to quantify the calcium present.
  • the method used to determine the amounts of surfactant (nonyl phenol ethoxylate) present in batches of WITCOBOND 740 emulsion involved soxhlet extraction with methanol of the films produced after drying. Followed by HPLC analysis on the extracts produced.
  • the malvern particle size analyser is a light scattering based particle size analyser. It uses a 2 milliwatt Helium/Neon laser and a Fourier transform lens system to focus the scattered laser light on to a photosensitive silicon detector.
  • the lens used was a 45mm lens which is used to measure particle diameters in the range of 0.1 to 80 ⁇ m.
  • the sample diluent was deionised water that had been filtered through a
  • the diluent particle size is measured prior to sample addition and is accounted for in the results as the background reading.
  • the sample dilution was one drop from the end of a microspatula per 500ml of diluent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à un procédé de fabrication d'articles élastomères à paroi mince, aux articles élastomères à paroi mince obtenus, ce procédé consistant à immerger un gabarit de forme appropriée dans une émulsion de polyuréthane renfermant un plastifiant et un diaryl sulfone-ester.
PCT/US1995/011765 1994-09-16 1995-09-15 Articles elastomeres WO1996008353A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9418684.8 1994-09-16
GB9418684A GB9418684D0 (en) 1994-09-16 1994-09-16 Elastomeric articles

Publications (1)

Publication Number Publication Date
WO1996008353A1 true WO1996008353A1 (fr) 1996-03-21

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GB (1) GB9418684D0 (fr)
WO (1) WO1996008353A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997047451A1 (fr) * 1996-06-13 1997-12-18 Lrc Products Limited Articles de polyurethane a parois minces et surface rugueuse et procede de production de ces derniers
EP1189524A1 (fr) * 1998-08-27 2002-03-27 John L. Gardon Articles medicaux et d'hygiene non-allergenes fabriques a partir d'elastomeres synthetiques reticules
WO2003103741A2 (fr) * 2002-06-07 2003-12-18 E.I. Du Pont De Nemours And Company Articles en polyurethane a paroi mince

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779975A (en) * 1971-12-13 1973-12-18 Witco Chemical Corp Sulfone-ester compounds as plasticizers for polyvinyl chloride resins
US3981945A (en) * 1973-11-19 1976-09-21 Imperial Chemical Industries Limited Coating compositions comprising a polysulfone and a fluorocarbon polymer
US3984604A (en) * 1970-06-19 1976-10-05 Imperial Chemical Industries Limited Aromatic polysulphone coated article and bonded structure
US4020046A (en) * 1970-06-19 1977-04-26 Imperial Chemical Industries Limited Aromatic polysulphone coated article and bonded structure
US4090993A (en) * 1975-07-29 1978-05-23 Imperial Chemical Industries Limited Coating compositions containing a mixture of a tetrafluoroethylene polymer an aromatic polyethersulfone
WO1981000346A1 (fr) * 1979-07-30 1981-02-19 American Hospital Supply Corp Gant de chirurgien et procede sans talc pour sa formation
US4425161A (en) * 1980-11-27 1984-01-10 Yutaka Shibahashi Thermochromic materials
US4463156A (en) * 1982-03-15 1984-07-31 Warner-Lambert Co., Inc. Polyurethane elastomer and an improved hypoallergenic polyurethane flexible glove prepared therefrom
US4901372A (en) * 1988-09-23 1990-02-20 Pierce William S Barrier surgical glove
US4919966A (en) * 1987-07-17 1990-04-24 Shlenker Robin R T Covering such as a glove, condom or sheath for inhibiting the spread of contagious diseases and methods of making and using the same
US4935260A (en) * 1987-07-17 1990-06-19 Shlenker Robin R T Covering such as a suit, glove, condum or sheath forming a chemical barrier against harmful agents and methods of making the same
US4947487A (en) * 1989-05-04 1990-08-14 The Jackson Laboratory Laser beam protective gloves
US5024852A (en) * 1987-08-20 1991-06-18 Hutchinson Process for preparing a prophylactic device made of rupturable microcapsules and layers of elastomeric material
US5051310A (en) * 1988-06-18 1991-09-24 Basf Aktiengesellschaft Textured polyurethane molded articles having multiple sheet layers
US5128168A (en) * 1987-07-17 1992-07-07 Robin R. T. Shlenker Method of forming a membrane, especially a latex membrane, having a biocide barrier
US5338565A (en) * 1987-07-17 1994-08-16 Robin R. T. Shlenker Method of forming a membrane, especially a latex membrane, having a biocide barrier
US5370900A (en) * 1992-10-05 1994-12-06 Johnson & Johnson Medical, Inc. Thin-fingered medical glove
US5399400A (en) * 1991-07-03 1995-03-21 Smith & Nephew, Inc. Elastomeric articles
US5436399A (en) * 1992-09-29 1995-07-25 Asahi Kasel Kogyo Kabushiki Kaisha Thermoplastic polyurethane derived from polytetramethylene carbonate diol

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984604A (en) * 1970-06-19 1976-10-05 Imperial Chemical Industries Limited Aromatic polysulphone coated article and bonded structure
US4020046A (en) * 1970-06-19 1977-04-26 Imperial Chemical Industries Limited Aromatic polysulphone coated article and bonded structure
US3779975A (en) * 1971-12-13 1973-12-18 Witco Chemical Corp Sulfone-ester compounds as plasticizers for polyvinyl chloride resins
US3981945A (en) * 1973-11-19 1976-09-21 Imperial Chemical Industries Limited Coating compositions comprising a polysulfone and a fluorocarbon polymer
USRE31448E (en) * 1973-11-19 1983-11-22 Imperial Chemical Industries, Ltd. Coating compositions comprising a polysulfone and fluorocarbon polymer
US4090993A (en) * 1975-07-29 1978-05-23 Imperial Chemical Industries Limited Coating compositions containing a mixture of a tetrafluoroethylene polymer an aromatic polyethersulfone
WO1981000346A1 (fr) * 1979-07-30 1981-02-19 American Hospital Supply Corp Gant de chirurgien et procede sans talc pour sa formation
US4425161A (en) * 1980-11-27 1984-01-10 Yutaka Shibahashi Thermochromic materials
US4463156A (en) * 1982-03-15 1984-07-31 Warner-Lambert Co., Inc. Polyurethane elastomer and an improved hypoallergenic polyurethane flexible glove prepared therefrom
US4919966A (en) * 1987-07-17 1990-04-24 Shlenker Robin R T Covering such as a glove, condom or sheath for inhibiting the spread of contagious diseases and methods of making and using the same
US4935260A (en) * 1987-07-17 1990-06-19 Shlenker Robin R T Covering such as a suit, glove, condum or sheath forming a chemical barrier against harmful agents and methods of making the same
US5128168A (en) * 1987-07-17 1992-07-07 Robin R. T. Shlenker Method of forming a membrane, especially a latex membrane, having a biocide barrier
US5338565A (en) * 1987-07-17 1994-08-16 Robin R. T. Shlenker Method of forming a membrane, especially a latex membrane, having a biocide barrier
US5024852A (en) * 1987-08-20 1991-06-18 Hutchinson Process for preparing a prophylactic device made of rupturable microcapsules and layers of elastomeric material
US5051310A (en) * 1988-06-18 1991-09-24 Basf Aktiengesellschaft Textured polyurethane molded articles having multiple sheet layers
US4901372A (en) * 1988-09-23 1990-02-20 Pierce William S Barrier surgical glove
US4947487A (en) * 1989-05-04 1990-08-14 The Jackson Laboratory Laser beam protective gloves
US5399400A (en) * 1991-07-03 1995-03-21 Smith & Nephew, Inc. Elastomeric articles
US5436399A (en) * 1992-09-29 1995-07-25 Asahi Kasel Kogyo Kabushiki Kaisha Thermoplastic polyurethane derived from polytetramethylene carbonate diol
US5370900A (en) * 1992-10-05 1994-12-06 Johnson & Johnson Medical, Inc. Thin-fingered medical glove

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997047451A1 (fr) * 1996-06-13 1997-12-18 Lrc Products Limited Articles de polyurethane a parois minces et surface rugueuse et procede de production de ces derniers
US6143416A (en) * 1996-06-13 2000-11-07 Lrc Products Limited Polyurethane thin-walled articles with a rough surface, and method of producing the same
EP1189524A1 (fr) * 1998-08-27 2002-03-27 John L. Gardon Articles medicaux et d'hygiene non-allergenes fabriques a partir d'elastomeres synthetiques reticules
WO2003103741A2 (fr) * 2002-06-07 2003-12-18 E.I. Du Pont De Nemours And Company Articles en polyurethane a paroi mince
US6720049B2 (en) 2002-06-07 2004-04-13 E. I. Du Pont De Nemours And Company Thin-walled polyurethane articles
WO2003103741A3 (fr) * 2002-06-07 2005-09-01 Invista Tech Sarl Articles en polyurethane a paroi mince

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Publication number Publication date
GB9418684D0 (en) 1994-11-02

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