MXPA97004915A - Flexible elastomeric articles and method for your manufacture - Google Patents

Abstract

In accordance with the present invention, a flexible article is provided, such as a surgeon's glove, which displays slip properties with respect to wet and dry mammalian tissue without the use of powdered lubricant, the article is composed of a substrate layer having an elastomeric material, the layer having a contact surface with the user and an amount conferring wet slippage of a lubricant composition applied to the user interface, the lubricant composition is selected from the group consisting of a first composition and a second composition, the first composition comprising an acetylenic diol and at least one compound selected from the group consisting of a modified silicone organ, an amino-modified silicone and a cationic surfactant, the second composition comprising a cationic surfactant and at least one compound selected from the group consisting of a sili modified convention, a modified amino silicone and an acetylenic diol, the elastomer can be natural or synthetic, and is preferably selected from the group consisting of natural rubber, a polyurethane, neoprene, nitrile rubber, a styrene-butadiene block copolymer, styrene, a styrene-isoprene-styrene block copolymer and combinations thereof: the cationic surfactant is preferably 1-hexadecylpyridinium monohydrate chloride

Description

FLEXIBLE ELASTOMERIC ARTICLES AND METHOD PORO ITS MANUFACTURE CROSS REFERENCE TO RELATED REQUEST This request is a continuation in part of the request of the U. A. copendiente series No., filed on June 28, 1996 and entitled "Elas ornen c Flexible Articles and Their Method of Manufacture", pending.

TECHNICAL FIELD This invention relates to flexible elastomeric articles (eg, film articles), particularly dust-free medical gloves that exhibit improved lubricity ("slippage") with respect to both dry and wet surfaces, particularly skin or other tissue of the wearer, in comparison with similar articles or films that are not treated as described herein. This invention also relates to a method for making said articles. This invention also relates to a lubricant composition and a method of treating elastomeric flexible articles with a lubricating composition.

BACKGROUND OF THE INVENTION The elastomeric surfaces of the articles, in general, exhibit poor lubricity with respect to a dry surface, such as dry skin or other mammalian tissue. These properties are due to surface friction. Additionally, many elastomeric articles or surfaces exhibit poor lubricity with respect to wet surfaces. A high coefficient of friction is a distinct disadvantage in those applications where an elastomeric surface should slide over another surface, such as in the placement of gloves on dry or wet skin. This is particularly important in the use of medical gloves, such as examination gloves and surgeon gloves. These gloves fit relatively tight to provide sensitivity. In addition, most surgeons put on their gloves after washing and without having completely dried their hands, so that their hands may be distinctly wet. Therefore, the elastomeric materials useful in such applications should exhibit improved lubricity with respect to dry surfaces ("dry slip"), improved lubricity with respect to wet surfaces ("wet slip"), and the mechanical properties required. The prior art has tried in various ways to produce dust-free gloves that meet these requirements. A previous approach is to halogenate the surface of rubber gloves with chlorine or bromine to make them slippery, that is, reduce the viscosity and increase the coefficient of friction of rubber gloves. In the case of chlorine as halogen, the prior art describes the production and use of chlorinated water to treat rubber gloves. Such methods include (1) direct injection of chlorine gas into the water mixture, (2) mixing high-density bleach powder and aluminum chloride in water, (3) brine electrolysis to produce chlorinated water, and (4) acid bleach. icado. See, for example, U.S. Patent Nos. 3,411,982 (Kavalir), 3,740,262 (Agostinelli), 3,992,221 (Hornsy, et al, treatment of the external surface with chlorine gas), 4,597,108 (Mornose), and 4,851,266 (Momose). However, chlorination produces surfaces that have very poor wet slippage. There are other rubber gloves of the prior art having a slip layer attached to the inner surface of said gloves. Examples of gloves having an inner layer of elastomeric material with particulate lubricant embedded therein are described in U.S. Patent Nos. 4,070,713 (Stockum), 4,143,109 (Stocku), 5,284,607 (Chen) and 5,395,666 (Brindle; surfactant, but ionic surfactants are not recommended), and which describe surgeon gloves with different polymeric slip coatings attached to the inner surface thereof are found in US Patent Nos. 3,813,695 (Podell et al. internal of hydrophilic plastic material, for example hydrogel polymer), 3,856,561 (E emplare, et al.; an inner layer of a copolymer of vinyl chloride or vinylidene and an alkyl acrylate), 4,302,852 (Doung), 4,482,577 (Toldstein, et al.), 4,499,154 (Darnes, et al., uses specific hydrogel polymers as the inner layer which after it is treated with a cationic surfactant or fatty amine) and 4,575,476 (Podell, et al., internal layer of hydrogel polymer treated with cationic, ammonic or nonionic surfactant). The foregoing differ from the present invention.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, a flexible article is provided which exhibits slip properties with respect to moist and dry mammalian tissue without the use of powdered lubricants. The article is comprised of a substrate layer having an elastomeric material; the layer has a contact surface with the user and an amount that confers wet slippage of a lubricant composition applied to the contact surface with the user. The lubricant composition is selected from the group consisting of a first composition and a second composition, wherein the first composition comprises an acetylenic diol and at least one compound selected from the group consisting of an organoisolated silicone, an amino silicone, modified, and a cationic surfactant, preferably 1-hexadecylpyridinium chloride monohydrate, and wherein the second composition comprises a cationic surfactant, preferably 1-hexadecylpyridinium chloride rnonohydrate, and at least one compound selected from the group consisting of a silicone. organo-modified, a silicone and a diol acetylene. In one embodiment, the article is a surgeon's glove. The elastomer can be natural or synthetic, and is preferably selected from the group consisting of natural rubber, a polyethene, a homopolymer of a conjugated diene, a copolymer of at least two conjugated dienes, a copolymer of at least? N conjugated diene and at least one vinyl monomer, and combinations thereof. The conjugated diene may contain heteroatoms, such conjugated dienes which have been halogenated, for example chloroprene. Preferred conjugated dienes include butadiene, isoprene and chloroprene. Preferred vinyl monomers include alkenylarene, for example styrene; alkyls, for example ethylene and propylene; and acrylonitrile. The term "combinations thereof" with respect to the elastomer includes physical combinations thereof in a single layer and combinations thereof in layers thereof, for example, a multilayer elastomeric article having a polyurethane layer formed on top of it. , and that adheres to, a natural rubber layer.

A flexible elastomeric article treatment method will also be provided. The method comprises: (a) cleaning the surface of the article by means of washing; (b) chlorinate the surface of the article; (c) neutralize the surface of the article and the residual chlorine; and (d) bringing the surface of the article with a lubricating composition. The lubricant composition is selected from a first composition and a second composition, wherein the first composition comprises an acetylenic diol and at least one compound selected from the group consisting of a silicone or a gano-modified, non-silicone modified silicone. , and a cationic surfactant, preferably 1-hexadecylpyridinium chloride monohydrate (also known as cetylpyridylium chloride), and wherein the second composition comprises a cationic surfactant, preferably l-hexadecylpyridinium chloride monohydrate, and at least one compound selected from group consisting of an organo-modified silicone, an amino-modified silicone, and an acetyl amine diol. If the article has been previously chlorinated, or does not require or permit chlorination, steps (b) and (c) can be eliminated. If a powder is not used as a mold release when the articles are made, the washing step (a) can be eliminated. The dust-free medical gloves treated with the lubricant composition provide superior lubricity with respect to wet or dry placement, compared to the current chlorinated surgical gloves on the market.

DETAILED DESCRIPTION OF THE INVENTION The invention contemplates flexible elastomeric articles including those adapted for use in partial or total contact with mammalian tissue, such as surgical, examination and dental gloves.; condoms, bandages, catheters, ureters, covers and incontinence devices covered and other film items. Additionally, materials that impart wet and dry slip can be provided on one or more surfaces of the article, including, but not limited to, the interior and / or exterior surface relative to the user, as appropriate under the circumstances of use. of each article. For the purposes of this description, the external surface of an article and, in particular, of a glove, is defined as that surface which becomes an external surface of the glove in the position of actual use when used. The inner surface is defined as that surface which is adjacent to the user's skin when it is used. The opposite is true in the case of a catheter or ureter: the external surface is the surface in contact with the tissue of the user. To avoid ambiguity, the term "contact surface with the user" will be used herein. "Fabric" includes skin or epithelium without limitation. The elastomer used in the substrate layer can be a natural or synthetic rubber. Without limitation, synthetic rubbers include polyurethane, a homopolymer of a conjugated diene, a copolymer of at least two conjugated dienes, a copolymer of at least one conjugated diene and at least one vinyl monomer, and combinations thereof. The conjugated dienes are preferably those containing from 4 to 8 carbon atoms. Examples of suitable conjugated dienes include: 1,3-butadiene (butadiene). 2- eti-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-entadiene (piperylene), 1,3-hexadiene, and the like. Conjugated dienes may contain heteroatoms. Said conjugated dienes include those which have been halogenated, for example chloroprene. Mixtures of said conjugated dienes can also be used. The preferred conjugated dienes are butadiene, isoprene and chloroprene. To prepare synthetic rubber, any other vinyl monomer can be used for the copolymerization with at least one conjugated diene, as long as the resulting copolymer is elastomeric. Without limitation, said vinyl monomers include alkyl, alkenyl, and acrylonitrile. The preferred alkyls are ethylene, propylene and butylene. Preferred alkenyl anes are onoalkenyl aneses. The term "onoalkenylarene" includes particularly those of the benzene series such as styrenes and their analogs and homologs including o-methylstyrene, p-methylstyrene, p-tert-butyethene, 1,3-dimethylstyrene, alpha-methyleneterene and other ring styrenes alkyls, particularly styrenes methylated in the ring, and other rnonoalkenyl polycyclic aromatic compounds such as vinylnaphthalene, vinylanthracene and the like. Preferred monoalkyl enylarenes are onocylarene onycyclics such as styrene and alpha-methyleneterene, and styrene is particularly preferred. The copolymers can be random, decreasing or block. If the copolymers are block copolymers, it will be understood that each of the blocks of elements may be a polymeric furnace, a random copolymer or a decreasing copolymer, while in each block it predominates by the usual class of monomers which characterize the block. For example, the alkenylarene block may comprise styrene / al-methyleneterene copolymer block or random or decreasing styrene / butadiene block copolymer as long as the alkenyl anes individually predominate. Preferred rubbers are natural rubber and synthetic rubber, including neoprene polyurethane, nitrile rubber, styrene and butadiene block copolymers, particularly a styrene-bistathane-styrene block copolymer, and styrene-block copolymers. Iterene, particularly a styrene-styrene-styrene block copolymer. Natural rubber and polyurethane are preferred, natural rubber being very preferred. The neoprene is a homopolymer of the chloroprene conjugated diene. The nitrile rubber is a copolymer of the conjugated diene butadiene and the vinyl monomer acrylonitrile. Block copolymers of alkenylarenee (blocks "A") and conjugated diene (blocks "B") are preferably network formers, ie, at least block A and at least block B. The simplest form of said block copolymer is ABA, which is a three block copolymer. In such synthetic rubber, the blocks A e.symmetallically incompatible with the B block or blocks, resulting in a rubber consisting of two phases.; A continuous elastomeric phase (blocks B) and a plastic phase eirnilar to glass that is basically discontinuous and hard (blocks A) of unnamed domains. These domains act as physical interleavers that hold the ends of many block copolymer chains. Since the block copolymers A-B-A have doe A blocks separated by a block B, the domain formation results in the effective closing of the B blocks and aus entanglements inherent in the poem by means of block As and forming a network structure. Said phenomenon allows the rubber A-B-A to behave like a conventionally vulcanized rubber containing dispersed reactive filler particles. These thermoplastic A-B-A rubbers are physically interwoven by the do inioe in a network structure as opposed to chemically entwined as a conventionally vulcanized rubber. As such, these polymers can be handled in thermoplastic forming equipment and are soluble in a variety of relatively low coefficient solvents. Additionally, when polymers of this type are used, the vulcanization step can be removed and, unlike the vulcanized waste rubbers, the waste from the treatment of this thermoplastic elastomer can be recirculated for later use. The block copolymers can be produced by any well known block polymerization or copolymerization process, including the well-known techniques of sequential monomer addition, the incremental monomer addition technique or the coupling technique, as illustrated for example in the Patents from US Nos. 3,251,905; 3,390,207; 3,598,887 and 4,219,627, the descriptions of which are incorporated herein by reference. As is well known in the art of block copolymers, the decreasing block of copolymer can be incorporated into the multi-block copolymer by copolymerizing a mixture of conjugated diene and alkenylarene monomers using the difference in their rates of copolymerization reactivity. Different patents define the copolymer preparation in multiple blocks containing decreasing copolymer blocks, including U.S. Patent Nos. 3,251,905; 3,265,765; 3,639,521 and 4,208,356, the descriptions of which are incorporated herein by reference. It should be noted that the polymers and copolymers described above can be easily prepared, if desired, by the methods discussed above. However, since many polymers and copolymers are commercially available, for example KRATON ™ polymers, available from Shell Oil Company, it is usually preferred to use the commercially available polymer, since it serves to reduce the number of treatment steps. involved in the whole procedure. The typical thickness of the elastomeric substrate layer for surgical gloves ranges from about 300 to about 400 microns, preferably from about 100 to about 350 microns. Surgical gloves tend to be about 150 microns in size and orthopedic gloves tend to be about 300 milligrams of age. The article is treated with a lubricant composition to impart wet slip properties to the flexible elastomeric article, which is substantially free of dust and is preferably chlorinated. Extend combinations of appropriate components. The first composition comprises (i.e. has at least) (1) an acetylenic diol and (2) at least one compound selected from the group consisting of organo-modified silicone, an arnino-digested silicone, and 1-hexadecylpyridinium chloride onohydrate. The second composition comprises (1) 1-hexadecylpyridinium chloride monohydrate and (2) at least one compound selected from the group consisting of a modified organo-silicon, a non-modified silicone., and an acetylenic diol. The lubricant composition is preferably an aqueous solution or dispersion. The compound 1-hexadecylpyridinium chloride monohydrate (CAS No. 6004-24-6) is a commercially available cationic surfactant. Other suitable cationic surfactants include those which comprise at least one lipophilic entity such as an alkyl, aralkyl, aryl or cycloalkyl group containing from 6 to 18 carbon aurora, and a hydrophilic entity such as an ammonium group eubetit. (for example, a tetraalkylammonium, pyridinium or eimilar group). The preferential counterion must be compatible with the user's tissue; it could be, for example, chloride or another halogen. Preferred cationic surfactants are ammonium quaternary compounds having at least one Cβ-Ciß hydrocarbyl group (alkyl, aryl, aralkyl or cycloalkyl); A preferred hydroxycarbyl group is a hexadecyl group. The hydrocarbyl group can be linked to a quaternary nitrogen atom that is part of a heterocyclic ring (such as a pyridine, morpholine or imidazoline ring). As mentioned above, a particularly preferred tenectant is hexadecylpyridinium chloride. Other suitable cationic surfactants include benzalkonium chlorides, hexadecyltriyl ethylammonium chloride, dodecylpyridinium chloride, the corresponding bromides, a hydroxyethyheptadecyl-1-idazolium halide, cocoalkyldimethylamidobetaine and cocoaminopropylbetaine. Mixtures of surfactants can also be used. The concentration of cationic surfactant, for example, the preferred cetylpyridinium chloride, is in the range of about 0.05% to about 2.5% in pee.

A scale of about 0.25% to about 0.75% in pee is preferred, eg, 0.5% cetylpyridinium chloride solution. The acetylenic diolee useful in the present invention are acetylenic tertiary glycols and the tertiary glycole acetylenic acid ethylene oxide adduct.

Preferably, the acetylenic diols used in the practice of the invention are structurally repreetened by the formula: R R3 Rl-C-C = C-C-R * H (0CH2CH2) ¡, 0 0 (CH2CH20) xH wherein Ri and R "are alkyl radicals containing from 3 to 10 carbon atoms, and R2 and R3 are selected from the group consisting of methyl and ethyl, and x, and have a sum in the" 0-60 inclusive "range , where y = x = 0 represents the tertiary acetylenic glycole. In the preferred case, Ri and R4 are alkyl radicals having 3 to 4 carbon atoms each and R2 and R3 are methyl group. Ploe axis and additional synthesis techniques for the manufacture of acetylenic dioecious compounds are described in the patent of US Pat. No. 3,268,593 (Carpenter et al.) And 3,293,191 (Carpenter et al.), Which are incorporated herein by reference. The acetylenic diols useful in the present invention preferably have a 10 carbon chain as backbone with a carbon-carbon triple bond in the middle portion with a hydroxyl group on the carbon atoms on either side of the triple bond. The combination of these groups produces a region of high electron density, making the molecule polar. There is also a highly branched symmetric group on each side of this region providing the molecule with two hydrophobic areas. The complete molecule has a hydrophobic-hydrophilic-hydrophobic structure, making it a good wetting agent or surface tension reducer. See 3. Schwartz et al. "Acetylenic diol-based additives help glove akers eet quality standards," Elastomerics, page 16-18, December 1989. Suitable acetylenic diolees include the following, available from Air Products and Chemicals, Inc. Allentown, PA : Surfynol "104 (2,4,7,9-tetramethyl-5-decin-4,7-diol), Surfynol * 104E (Surfynol® 104 / ethylene glycol, 50/50), Surfynol * 440 (Surfynol® 104 + 3.5 oz. ethylene oxide), Surfynol * 465 (Surfynol * 104 + 10 moles of ethylene oxide) and Dynol * 605 (a mixture of ethoxylated acetylenic diols).

Acetylenic dioles are preferably ethoxylated acetylenic diols such as lae seriese Dynol® 604 and Surfynol® 400, available from Air Products and Chemical Inc., Allentown, Pennsylvania. Dynol * 604 is preferred because it provides better lubricity. The acetylenic diol is used in the form of a solution, such as an aqueous solution containing at least 0.01% in peeo haeta, for example, 2% in acetylene dioleum. The acetylenic diols can be used in a mixture or in combination. The modified eyliconnes in the present invention are hydrophilic, non-ionic eicicones. Examples of such silicone ee are commercially available from Oai Specialties, Inc., Danbury, Connecticut; are NuUet "100, NuUet-R 300 and NuUet * 500. NuUet® 100 is a copolymer described as an organo-modified polydirylethyloxane, more specifically, a polyalkylene oxide-modified polydimethylsiloxane NuUiet" 300 is also a copolymer described as a copolymer of silicone and amino-modified polyether. As a result of the amino modification, this material has a reportable amount of an alkanolamine. NuUet® 500 is a mixture of an organo modified polydi ethylsiloxane (> 65%) and an ethoxylated alkyl (< 20X). There are reportable amounts of ethylene oxide (<20%, the highest concentration bound by MSD Sheet is 0.0002X). The following table provides some physical properties for these three materials.

«Closed cup Peneky-Martene ASTM D-93.

According to the OSi product bulletin, the following non-aqueous diluents have been found useful: ethylene-ethylene propylene oxide polymer (Ucon 50HB 100, Carbide Union) methyl eoyate (Emery 2235, Henkel). methyl oleate (Emereet 2301, Henkel), methyl canolate (Emery 2231, Henkel), propylene carbonate (Arco), oleyl alcohol (Novol, Croda). To prepare solvents or solutions with materials, OSi recommends emptying the silicone in the whirlpool of the total water while mixing at a moderate speed (approximately 300 rpm to approximately 400 rpm). The mixture is continued until a uniform solution or viscosity is obtained. The non-aqueous solutions or dispersions are prepared in a similar manner, but measuring at approximately 150 rpm until approximately 200 rprn until a clear mixture is obtained. The Patentee de loe E. U. A. Nos. 4,690,955 (Kilgour et otroe); 4,769,174 (Kilgour); 4,847,398 (Mehta et al.) And 4,857,583 (Auetin et al.), Describe organo-modified polysiloxane varioe copolymers (ie, organo-modified silicones) and methods for making them. Said copolymers contain hydroxyl group. The arnino modification can be effected by first replacing the hydroxyl group with a halide. The halide can be reacted intonace with ammonia or an amine to replace the halogenide p > or an amino group. This last procedure is called halogenuroe ammonolie. Alternatively, polysiloxanes can be prepared to non-modified (ie, silicones to ino-modified), according to US Patent No. 3,905,823 (Pietoki), which is incorporated herein by reference. In these, amino-modified polysiloxanes are prepared by mixing an organo-modified polysiloxane (i.e., organo-modified eicicon) with silanes to inofunctional or siloxanes and then balancing the mixture in the presence of a basic catalyst, eg, hydroxides, alkoxides, hydrides, alkyls, alkenyls and aryls of alkali metal, and eilanoate. The modified eylicon is usually in the form of an eolion, such as an aqueous solution containing at least 0.05% pee to, eg, 5% pee of the modified silicone. The coating of the lubricant composition does not need to completely cover the surface that makes contact with the tank. It is only necessary to apply enough lubricant composition to increase the wet slip. It is preferred, insofar as it can be practiced, to keep the lubricant composition on the surface contacting the user, in the case of medical or dental gloves, to ensure that maximum grip is maintained on the external surface. The lubricant composition can be applied as an aqueous solution containing from about 0.2 to about 2% by weight with respect to the total lubricant composition. The article can be submerged in this solution or the solution can be sprayed or painted on it, before removing it from the form. Alternatively, the lubricant composition can be applied after the article has detached from the shape.

The method for applying the particle-containing coating to the surface of the elastomeric eubetratum that makes contact with the user depends in part on the nature of the eubetrate and whether the glove or other article is formed by immersing a form in an elatomeric polymer latex. or in a solution of the elastomeric polymer in a suitable solvent. The method for making the elastomeric substrate articles of the present invention is well known in the art. Where the article is made from the combined natural rubber latex, the deposit on the form is applied and leached in the normal manner and then dry and vulcanized. It is contemplated that the coating will normally be applied by immersing substantially the tank on the aqueous form of the revealing material, ie, the binder and the microparticles. The deposit and revetment can then be heated to dry them and complete the vulcanization of the rubber. Other substrate polymers in the disperea form e.g., latex, including polyurethane, can be treated in a similar manner, although the vulcanization step will not be necessary in each case, as can be readily appreciated by those skilled in the art. It is understood that several optional ingredients may be incorporated into these articles as is apparent to those skilled in the art. For example, where the article is a glove, an anti-blocking agent can be used to facilitate manufacturing and processing. The antiblock agent is preferably a wax of low melting point (m.p. of about 100 ° C at about 150 ° C). Such as polyethylene wax added with an aqueous solution (e.g., 1-2%) to the revetment mixture. The particle size of the wax should preferably be less than one miera to avoid interference with the surface morphology. According to the present invention, a method of a continuous process for making a powder glove comprises a summary form: (i) Reveai by immersing a coagulant on a glove shape; (ii) Immerse a layer of an elatomer by immersion in the coagulant layer; (iii) Leaching the elatomer article in the hot water; (iv) Heal the elatórnero with heat; (v) Chill the glove; (vi) Neutralize the glove and residual chlorine; (vii) Rinse the glove; (viii) Treat the glove with a lubricant composition; (ix) Dry the glove treated with lubricant; and (x) Remove the glove from the forrna, inverting the glove.

If the elastomer will not be chlorinated, steps (v) - (vii) can be omitted. According to the present invention, another embodiment of the process for making a powder glove comprises in order to recover: (a) General procedure for making dust-coated gloves: (i) Revetir by inert a coagulant on a form of guide; (ii) Revect by immersion on the coagulant layer a layer of an elastomer; (iii) Leaching the elastomer article in the hot water; (iv) Curing the elastomer with heat (v) Coating by starch a suspension of starch on the cured elastomer; and (vi) Remove the glove from the shape and invert the glove. (b) Off-line chlorination of the dusted glove followed by treatment with the lubricant composition. (i) Invert and wash the dusted glove; (ii) Chill the glove; (iii) Neutralize the glove and residual chlorine; (iv) Rinse the glove; (v) Treat the glove with a lubricating composition; (vi) Dry the glove treated with lubricant; and (vii) Invest and re-dry the glove. The application of the lubricant solution provides the glove with a powder, chlorinated, of lubricity euperior with repect to the wet / damp hand. The parts of part (a) e may omit if disposed gloves are available. Also, if chlorinated gloves are available, steps (b) (ii) - (iv) may be omitted. In an extended manner, the paoe for a modality of the present invention are described below. First, exempt a cleaning step to clean, for example, the hand shape, typically made of porcelain, to remove waste of previous manufacturing iteracionee. The clean form is then used to remove water residue by transporting the form through a preheated oven to evaporate the water. The preheated form is then coated by inmerion in a bath containing a coagulant, a powder source and a surfactant. The coagulant preferably contains calcium ions to break up the protection of the emulsion, thus allowing the latex to deposit on the form. The powder is preferably a calcium carbonate powder which subsequently acts as a releasing agent, alternatively, the powder source can be omitted using the combination of lipophilic compound and surfactant in the coagulant to help separate the glove according to the Patent. from the USA No. 4,310,929 to Jourg. The surfactant provides good moisture to avoid forming a meniscus and trapping air between the shape and the deposited latex, particularly in the fist area, an example of said surfactant with an acetylene d ol. As indicated above, the form has been preheated in the drying stage and the heat is returned to the water leaving calcium nitrate calcium carbonate powder and surface active agent on the surface of the form. The lined outer shell is immersed in a tank containing latex. The latex contains, for example, natural rubber latex in addition to stabilizing, antioxidant, activating, accelerating and vulcanizing, and these last being in powder form. The stabilizers are preferably surfactants of the phosphate type. The antioxidants are preferably of the phenol type, for example, antioxidant 2246 (2,2'-methylenebis (4-rnethyl-6-t-butylphenol) available from PMC Specialty Group, Fords, N. The activator can be, for example, Zinc oxide The accelerator can be, for example, dithiocarbate.The vulcanizer is preferably sulfur or a sulfur-containing compound.If these materials are used, the stabilizer, antioxidant, activator, accelerator and vulcanizer are dispelled in water to avoid The formation of lumps using a ball mill or a rubbing machine, in dispersion, then mixing in the latex, an emulsifying wax, which is used as an anionic, is then added to the latex mixture. it is immersed in the composition of the latex with the thickness of latex deposited thereon controlled by the duration of the inmeretion (in a given situation of inmereion). Eeta ee of about 5 to about 20 seconds, eg, about 12 hours. for a surgical glove; and from about 20 to 70 seconds, e.g., about 50 seconds, for an orthopedic glove. The form now coated with latex is immersed in a leaching tank in which hot water is circulated to leach all the water-soluble components, for example, calcium nitrates and reeidual proteins contained in the natural latex. This leaching process can continue for approximately 12 minutes with the tank at approximately 48.8 ° C. The shape is then extracted from the leaching bath to a flange and printing station. For this purpose, a flange is formed around the cuff area at the end of the coiled mechanical glove of the upper portion or end portion of the glove at a predetermined amount. The logos of the company, the size and a traceable date of manufacture are printed on the outside of the glove, for example, by injecting ink into the latex replenishment on the form. The latex-lined form is then sent to a cure station where the natural rubber in the form re-form is typically vulcanized in an oven, thereby curing the rubber. The curing station initially evaporates any remaining water in the latex of the form and then proceeds to the vulcanization of higher temperature. The etching may occur between 87.7 ° C to 93.3 ° C with a vulcanization step occurring at temperatures, for example, from about 104 ° C to about 115.5 ° C. This overall procedure can last around 40 to 45 minutes in total. For example, the furnace may be divided into four different zones with a shape being conveyed through the increasing temperature zone. An example is a furnace having four zones with the first doe zones being indicated for drying and the second being zoneped mainly by the vulcanization step. Each of the zone may have a slightly higher temperature, for example, the first zone at about 82.2 ° C, the second zone at about 93.3 ° C, a third zone at about 104.4 ° C and a final zone at about 115.5 ° C. The residence time of the form within an area in this case is about 10 minutes approximately. The accelerator and vulcanizer contained in the latex that contains the forrna are used to intertwine the natural rubber in the bundle. The vulcanizer forms sulphide bonds between different rubber segments and the accelerator ee uea so that the formation of sulfur bridges proceeds more quickly. The shape that now has a rubber glove cured on it is then immersed in a suspension of starch. Gloves that contain dust can be removed and packaged at this time. The suepeneion has starch and eylicon to improve, for example, the putting of the conventional glove on the hand of a person. The starch is preferably starch entangled with epichloridine. Silicone is also used to treat or prevent blockage during the removal of the glove from the shape and to help place it in a dry hand. Therefore, the glove will have a starch powder on the surface that is fixed to the miamo. After that, the glove is separated from the shape that inverts the glove with the interior now being outside and viceverea. Are the glove sizes distributed and inspected for each other? adequacy. The above paoe are used in the manufacture of a glove containing powder of the prior art to assist placement in the hand of a user. Instead of doing this glove, said prior art gloves can be obtained and discussed in the following manner. Eetoe g? Antee sprinkled after they are inverted again from the inside out and therefore are in the orientation in which the glove was before separating it from the form. The inverted glove is then washed to remove dust and starch from the glove. The washing is carried out with tap water at room temperature and then repeated as necessary. The washed gloves are then chlorinated. If a continuous procedure is used, the cured gloves that leave the curing station and optionally still over the chlorinated form and the intervention steps eon orni * Ldoe. Chlorination, or very generally halogenation, can be formed in any suitable manner known to those skilled in the art. These methods include (1) direct injection of chlorine gas into the water mixture, (2) mixing of high-density bleaching powder and aluminum chloride in water, (3) electrolyze of the brine to produce chlorinated water, and (4) bleach. acidified. See, for example, US Patents. Noe 3,411,982 (Kavalir), 3,740,262 (Agoetinelli), 3,992,221 (Horney, and other; however, it is modified to treat the surface of contact with the user, instead of treating the exterior surface with gaseous chlorine), 4,597,108 (Momoee), and 4,851,266 (Mornoee). A preferred method is to inject chlorine gas into a stream of water and then feed the chlorinated water into a greaser (a closed container) containing the glove and wash. The concentration of chlorine can be monitored and controlled in order to control the degree of chlorination. The chlorine concentration is typically at least about 500 ppm, preferably about 500 ppm to approximately 1,200 ppm, e.g., about 800 ppm. The duration of the chlorination step can also be controlled in order to control the degree of chlorination. The duration may vary from about 3 to about 20 minutes, e.g., 7 minutes. The glove that is in a flattened state will be chlorinated to a greater degree on the surface contacting the,? Ary, ie, the glove's side of the glove, with a smaller amount on the side of the glove that is not on the side. of pueeta. In another preferred method, the gloves can be chlorinated by placing them in a grenadier, including a front-loading indi-vidual washer, which contains a water bath containing a bleach which is eequently acidified to a pH of 2 to about 3. The concentration of chlorine ranges from about 0.05 to about 0.3% in peo, e.g., of about 0.1% in peeo. The duration varies from around 3 to about 25 minutes. Again, the putting side of the glove will have a greater amount of chlorination than the side that does not wear the glove. For a higher degree of chlorination on the non-glove side, the gloves should be inverted and the chlorination step repeated. The acidified bleach is then preferably neutralized with ammonium hydroxide or eioxide thiosulfate. This step neutralizes the acidified water contained in the gilder and extinguishes the excess of chlorine to ammonium chloride, and ammonium hydroxide is used. Even inside the industrial washer, the chlorinated gloves are then rinsed with tap water at about room temperature. This rinse cycle can be repeated as necessary. Once all the water has been removed from the front loading washer, the glovers are subjected to centrifugation to drain the excess water.

A lubricious solution adds deep to the glove containing the greaser that is supposed to be removed for approximately 5 minutes. This reverses the side of the + a with the lubricating solution. The lubricant solution is drained from the greaser and then used again. If it is used again, the lubricating solution preferably returns once again. The coated guans are placed in a dryer and dried for approximately 10 to 15 minutes at a temperature of approximately 43.5 ° C to dry the laying surfaces. The gloves are re-inverted deep and the side that has not been used for approximately 25 minutes at a temperature of about 48.8 ° C. The foregoing shows a sequence of events of the manufacture of gloves according to the present invention. If the gloves are available or the chlorinated gloves are available, some of the above steps can be eliminated and the process can be started in the proper procedure.

EXAMPLES In the following examples and comparative axis, the following additional product designations are used: NeoRezR XR-9624 is a dielectric dierephine of dielectrically aliphatic polyurethane from Zeneca Reeine (formerly of ICI Reeine), Uilmington, Massachusette. VedocR VP180 is a polyester-based polyurethane powder.

EXAMPLE I The dusted glove is manufactured with the general procedure described in the detailed description section of the invention. The out-of-line chlorination of the glove dusted to produce a dustless glove is done in the following sequence: (1) invert and wash the dusted glove; (2) chlorinate the washed glove; (3) neutralize the glove and residual chlorine; (4) rinse the chlorinated and neutralized glove; (5) extract to remove excess water from the glove; (6) The chlorinated glove is then treated with the following lubricant formulation: (7) After treatment with lubricant, the glove treated with lubricant is dry; (8) invert and re-dry the glove treated with lubricant. It is found that the finished glove has no loose powder and has superior lubricity with respect to wet / wet setting.

EXAMPLE II In accordance with the general procedure of example I, a glove is formed using the following lubricant formulation: It is found that the finished glove has no loose powder and has superior lubricity with respect to the wet / damp seat.

EXAMPLE III In accordance with the general procedure of Example I, a glove is formed using the following lubricant formulation: It is found that the finished glove has no loose powder and has superior lubricity with respect to wet / wet tile.

EXAMPLE IV A layer of natural rubber latex is applied to an average temperature of 150 microns over a glove shape that is eemerged in the following antiblocking coating formulation: A layer of the formulation is deposited on the natural water latex layer. The layers are then cured and submerged in a starch suspension. The glove is deep in the shape of a way that invests the glove. A method for making a reverend glove with polymer suitable for use in connection with this invention is described in US Pat. No. 5,284,607. Off-line chlorination and lubricant treatment in the above glove is carried out in accordance with the general procedure of Example I. It is found that the finished glove has no loose powder and has superior lubricity with respect to the wet / wet outline . The present invention has been described primarily with respect to surgeon's glove. As originally indicated, the present invention is also applicable to other items elaeto ericoe flexiblee of skin contact or reagent, such as condoms, gloves worn by veterinarians and surgeons and veterinarians for examination purposes (such glove often standing with dry hands) catheters, ureters, sheets, covers and dispoeitivo for incontinence type of cover. When the present invention is used for articles such as ureters and catheter, the outer surface is coated with the lubricating composition (the surface being contact with the eardrum being eeta); for condonee, the inner and / or outer surface can be treated with the lubricant composition.

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A method of treating a flexible elatomeric article, the article comprising: treating the surface of the article with a lubricant composition, wherein the lubricant composition is selected from the group consisting of a first composition and a second composition, wherein the first composition it comprises an acetylenic diol and at least one compound selected from the group consisting of an organo-modified ailicon, a non-modified eylicon and a cationic surfactant, and wherein the second composition comprises a cationic surfactant and at least one compound selected from the group consisting of an organo-modified eylicon, an amino-modified eylicon and an acetylenic diol.

2. A method according to claim 1, further characterized in that the cationic surfactant is 1-hexadecylpyridinium chloride monohydrate.

3. A method according to claim 1, characterized in that before the treatment step the method comprises: chlorinating the surface of the article; and neutralize the surface of the article and reeidual chlorine.

4. A flexible elastomeric article having a contact surface with the user in which a lubricant composition has been applied to the contact surface with the user to eubstantially improve the lubricity of the surface with respect to wet skin, where The lubricant composition is selected from the group connecting a first composition and a second composition, wherein the first composition comprises an acetylene-free diol and at least one compound selected from the group which connects an organo-modified eylicon, a an ino-modified product and a cationic surface active agent, and wherein the second composition comprises a cationic surface active agent and at least one component selected from the linking group of an organo-modified eylicon, an amino-modified silicone and an acetylene diol. .

5. An article according to claim 4, further characterized in that the article is a surgeon's glove.

6. An article according to claim 4, further characterized in that the cationic surfactant is 1-hexadecylpyridinium chloride monohydrate.

7. A flexible article that displays sliding properties with respect to wet and dry mammalian fabric without the use of powdered lubricants comprising: a layer of sub-layer comprising an elastomeric material, the layer having a surface of contact with the user; and an amount conferring wet slippage of a lubricant composition applied to the contact surface with the user, wherein the lubricant composition is selected from the linking group of a first composition and a second composition, wherein the first composition comprises a diol. acetylenic and at least one co-selected from the connecting group of an organo-modified organolean, an arnino-modified ailicon, and a cationic surface active agent, and wherein the second composition comprises a cationic surfactant and at least one selected component. of the group consisting of an organo-modified eilicon, an amino-modified ailicon and an acetylenic diol. 8.- An article in accordance with the claim 7, further characterized in that the article is a surgeon's glove. 9. An article according to claim 7, further characterized in that the ionic cationic surfactant is 1-hexadecyl-iridinium chloride monohydrate. 10. An article according to claim 7, further characterized in that the elastomer is selected from the group consisting of natural rubber, a polyurethane, a homopolymer of a conjugated diene, a copolymer of at least two conjugated dienes, a copolymer of at least one conjugated diene and at least one vinyl monomer, and combinations of the miarnos. 11. An article according to claim 10, characterized in that the elatomer is natural rubber. 12.- An article in accordance with the claim 10, further characterized in that the elastomer is a polyurethane. 13. An article in accordance with the claim 10, characterized in that the article has a first elastomeric layer and a second elastomeric layer, and that the elastomer for the first elastomeric layer is natural rubber and the elatomer for the second elatomeric layer is polyurethane. 14. An article according to claim 10, characterized in that the elatomer is a polymethylamine or conjugated diene furnace. 15. An article in accordance with the claim 14, characterized in that the elastomer is neoprene. 16. An article according to claim 14, characterized in that the conjugated diene is isoprene. 17. An article according to claim 10, characterized in that the elatomer is a copolymer of at least one conjugated diene and at least one vinyl monomer. 1

8. An article according to claim 17, characterized in that the elatomer is nitrile rubber. 1

9. An article according to claim 17, further characterized in that the elastomer is a block copolymer of etherene-ieoprene-ethene. 20. An article according to claim 17, further characterized in that the elastomer is a styrene-butadiene-styrene block copolymer. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a flexible article, such as a surgeon's glove, which extends deep-seating properties with respect to wet tissue and mammalian tissue without the powder coating agent; the article is composed of a layer of substrate having an elastomeric material, the layer having an interface with the user and a quantity that confers wet reaming of a lubricant composition applied to the contact surface with the user; The lubricant composition is selected from the group which contains a first composition and a second composition; the first composition comprises an acetylenic diol and at least one composition selected from the group consisting of an organo-modified silicone, an amino-modified silicone and a cationic teneoactive agent; the second composition comprises a cationic surfactant and at least one compound selected from the group consisting of an organo-modified silicone, an amino-modified silicone and an acetonic diol; the elatomer may be natural or synthetic, and is preferably selected from the group consisting of natural rubber, a polyurethane, neoprene ,. nitrile rubber, an eetirene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer and combinations of the mieme; the cationic surfactant is preferably 1-hetacyl pyridinium chloride monohydrate. EA / JJ / mmrn * avc * lprn P97 / 672