CA2097408C - Flexible rubber article and method of making - Google Patents
Flexible rubber article and method of making Download PDFInfo
- Publication number
- CA2097408C CA2097408C CA 2097408 CA2097408A CA2097408C CA 2097408 C CA2097408 C CA 2097408C CA 2097408 CA2097408 CA 2097408 CA 2097408 A CA2097408 A CA 2097408A CA 2097408 C CA2097408 C CA 2097408C
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- Canada
- Prior art keywords
- layer
- natural rubber
- film
- bath
- glove
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B42/00—Surgical gloves; Finger-stalls specially adapted for surgery; Devices for handling or treatment thereof
-
- 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
-
- 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
- B29C41/22—Making multilayered or multicoloured articles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31569—Next to natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
- Y10T428/3183—Next to second layer of natural rubber
Abstract
ABSTRACT
A multi-layer flexible article includes a first layer of natural rubber, a second layer of natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethylene oxide and a third layer of acrylic copolymer and fluorocarbon telomer resin. The article is preferably a glove formed by the method of dipping a hand shaped mold into baths containing aqueous emulsions of the components used to form the layers. Gloves manufactured according to the method are substantially wet-hand and dry-hand donnable as compared to powdered latex gloves of similar size.
The finished gloved is water washed and wet autoclaved to substantially reduce the protein content from the natural rubber and substantially remove other water extractable allergenic moieties. The washing and autoclaving renders the glove substantially hypoallergenic as compared to gloves not so treated.
A multi-layer flexible article includes a first layer of natural rubber, a second layer of natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethylene oxide and a third layer of acrylic copolymer and fluorocarbon telomer resin. The article is preferably a glove formed by the method of dipping a hand shaped mold into baths containing aqueous emulsions of the components used to form the layers. Gloves manufactured according to the method are substantially wet-hand and dry-hand donnable as compared to powdered latex gloves of similar size.
The finished gloved is water washed and wet autoclaved to substantially reduce the protein content from the natural rubber and substantially remove other water extractable allergenic moieties. The washing and autoclaving renders the glove substantially hypoallergenic as compared to gloves not so treated.
Description
~p~ ;s~ E39~93~l~90 urf 0,:l992 2 ~
P-~274 (0115a) FLEXIBLE RUBBER ARTICLE ANI) METHOD OF MAKING
Field of Invention This invention relates to flexible rubber articles and more particularly to rubber surgeon's gloves and the method of making same.
Backqround of the Invention Flexible surgeon's gloves have very demanding requirements. They should have strength to resist tearing and should be thin and flexible to allow touch sensitivity. Further, they should be easy to don with wet or dry hands, but not be slippery for handling instruments.
Traditionally, surgeon's gloves have been manufactured by dipping molds or forms shaped like hands into baths containing natural rubber latex emulsions to form a film of the desired thickness. The film is then cured and the glove is removed from the mold. There are numerous problems with the manufacture and use of natural rubber gloves, an important one of which is the step of removal from the mold form. Removal from the mold can be difficult because the cured latex tends to be tacky and may adhere to the mold. Further, plain natural rubber latex gloves adhere to thèmselves and tend to be very difficult for a surgeon to don. This is particularly true in actual use situations where a sterility pro~ocol is followed with the surgeon having wet hands. Techniques for addressing these problems have developed - - .
~ , ' P-227~ -2- 2~7~
over the years. Initially, mold-release powders wer~ dusted onto the surface of the mold forms to facilitate the removal of the glove from the form. Since the gloves are generally turned inside out as they are stripped from the form, these powders then aided the subsequent donning of the glove by the surgeon.
A wide variety of powders including talc, lycopodium, calcium carbonate, starch and modified starches has been used.
Problems were identified with granuloma formation in patients and attributed to powders, particularly talc and its use has long been abandoned. Powdered gloves are still widely accepted today with epichlorohydrin modified starches being used quite successfully as powders for gloves by carefully controlling the material used and the amounts present on each glove.
As an alternate to powder, there are many disclosures o coating or treatments of gloves to modify their surface properties. These surface modifications have enjoyed varying degrees of success, as high guality powdered gloves are still considered optimum in terms of strength, tactility and ease of donning and removal.
There are two general ways of achieving natural rubber latex gloves which do not require powder for donning, chemical treatment of the rubber surface and adding materials onto a natural rubber surface. Representative of the chemical treatment is halogenation. Halogenation renders a rubber surface slippery, but it is most effective in conjunction with dry hands and additionally, the treatment may weaken and embrittle the overall film. It may also adversely affect the shelf life of a sterile glove.
There are many disclosures relating to adding materials to a rubber surface to improve its slip characteristics with both wet and dry skin. Representative of the disclosures is United States Patent 4,575,476 to Podell et al. Podell et al. teaches a dipped rubber article having a skin contacting surface layer formed of a hydrogel polymer, such as polyvinyl pyrrolidone, , .. . . .. . .
. ::
P-227~
P-~274 (0115a) FLEXIBLE RUBBER ARTICLE ANI) METHOD OF MAKING
Field of Invention This invention relates to flexible rubber articles and more particularly to rubber surgeon's gloves and the method of making same.
Backqround of the Invention Flexible surgeon's gloves have very demanding requirements. They should have strength to resist tearing and should be thin and flexible to allow touch sensitivity. Further, they should be easy to don with wet or dry hands, but not be slippery for handling instruments.
Traditionally, surgeon's gloves have been manufactured by dipping molds or forms shaped like hands into baths containing natural rubber latex emulsions to form a film of the desired thickness. The film is then cured and the glove is removed from the mold. There are numerous problems with the manufacture and use of natural rubber gloves, an important one of which is the step of removal from the mold form. Removal from the mold can be difficult because the cured latex tends to be tacky and may adhere to the mold. Further, plain natural rubber latex gloves adhere to thèmselves and tend to be very difficult for a surgeon to don. This is particularly true in actual use situations where a sterility pro~ocol is followed with the surgeon having wet hands. Techniques for addressing these problems have developed - - .
~ , ' P-227~ -2- 2~7~
over the years. Initially, mold-release powders wer~ dusted onto the surface of the mold forms to facilitate the removal of the glove from the form. Since the gloves are generally turned inside out as they are stripped from the form, these powders then aided the subsequent donning of the glove by the surgeon.
A wide variety of powders including talc, lycopodium, calcium carbonate, starch and modified starches has been used.
Problems were identified with granuloma formation in patients and attributed to powders, particularly talc and its use has long been abandoned. Powdered gloves are still widely accepted today with epichlorohydrin modified starches being used quite successfully as powders for gloves by carefully controlling the material used and the amounts present on each glove.
As an alternate to powder, there are many disclosures o coating or treatments of gloves to modify their surface properties. These surface modifications have enjoyed varying degrees of success, as high guality powdered gloves are still considered optimum in terms of strength, tactility and ease of donning and removal.
There are two general ways of achieving natural rubber latex gloves which do not require powder for donning, chemical treatment of the rubber surface and adding materials onto a natural rubber surface. Representative of the chemical treatment is halogenation. Halogenation renders a rubber surface slippery, but it is most effective in conjunction with dry hands and additionally, the treatment may weaken and embrittle the overall film. It may also adversely affect the shelf life of a sterile glove.
There are many disclosures relating to adding materials to a rubber surface to improve its slip characteristics with both wet and dry skin. Representative of the disclosures is United States Patent 4,575,476 to Podell et al. Podell et al. teaches a dipped rubber article having a skin contacting surface layer formed of a hydrogel polymer, such as polyvinyl pyrrolidone, , .. . . .. . .
. ::
P-227~
-3- 2~
polyhydroxye-thyl acrylate or methacrylate and copolymers of these with each other or with acrylic or methacrylic acid, or with 2-ethylhe~yl acrylate or a ternary copolymer of 2-hydroxyethyl methacrylate, me-thacrylic acid and 2-ethylhexyl acrylate.
Gloves prepared according to the teaching of Podell et al.
can be shown to have less mechanical streng-th and reduced resistance to accelerated aging after sterilization compared to conventional powdered latex gloves. Under conditions of mechanical stress, such as extreme elongation as could occur during donning, they may partially delaminate and los0 particles from the hydrogel coating. Further, they tend to be some wha-t thicker than many powdered latex gloves thereby adversely affecting tactile sensitivity.
Summary of the Invention A multi layer flexible article includes a first layer formed from natural rubber. A second layer is formed from natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethylene oxide. A third layer is formed of acrylic copolymer and fluorocarbon telomer resin.
The article preferably may be a multi-layer surgeon's glove formed by dipping a hand shaped mold form in a series of baths.
The preferred gloves are wet hand and dry hand donnable without the need for powder, and have greater strength compared to existing gloves of similar thickness. The structure of the gloves substantially reduces the incidence of air pinhole defects in manufacture of the gloves when compared to natural rubber latex gloves of similar thickness.
A method for manufacturing multi-layer articles, preferably gloves, includes dipping a hand shaped mold form in a series of baths to form on the surface of the mold, a patient contacting first layer of natural rubber, a wearer contacting layer of acrylic copolymer and fluorocarbon telomer and, intermediate to the wearer and patient contacting layers, a layer including ~ . .
`: :
! " ' .
P--227~ 2~9~
natural rubber, polyurethane, poly(acrylamicle/acrylic acid) and polyethylene oxide. The layers are washed, dried and cured to form a unitary structure, then the st:ructure is everted as it is removed from the mold as a finished glove. The glove preferably then has a coating of lubricant applied to the surface, preferably followed by water washing, wet autoclaving and drying.
Detailed Description In accordance with the present invention, a preferred embodiment is a surgeon's glove formed on the surface of a mold.
The manufacture begins with a surface of a cleaned and coagulant treated mold form which is coated by dipping the mold in a bath containing a natural latex rubber emulsion.
The glove molds are individual for the right and left hands. The molds are made in a variety of si~es and shapes corresponding to the various hand sizes for which the gloves are intended. The molds are preferably made of ceramic, most preferably porcelain, bisque or glazed, but other materials such as stainless steel, glass, hard woods and plastic may also be used.
Suitable coagulants include, but are not limited to, calcium nitrate, calcium chloride, acetic acid, magnesium acetate, and the like. A bath with an aqueous solution of about 20 to 25%, preferably 22.5%, calcium chloride with about 0.1 to 0.2% octoxynol, preerably 0.15%, is preferred for coating the i molds with coagulant.
When the mold is dipped in the latex bath, the latex forms a patient contacting film on the surface of the coagulant coated mold which serves as a substrate for subsequent layers. The thickness of the substrate film and the subsequently applied layers is generally governed by the solids content of the emulsions, the quantity of the coagulant deposited on the mold, the temperature of the mold and the residence time of the mold in the baths.
P-227~ 2~
In a preferred embodiment, where the substra~e is formed from natural rubber latex, the porcelain molds are cleaned in a bath with aqueous sodium hypochlori-te of concentration about 2.5 to 5%, preferably 3.0%, then rinsed with 120 to 150F., preferably 135~F., water and allowed to drain. The rinsed and drained molds are then dipped in the calcium chloride coagulant bath with a temperature preferably about 110 to 130F., most preferably 120F. The molds with the coagulant on their surace are dried at about 210 to 270F. for about 8 to 10 mi.nutes, preferably 250 F. for 8.5 minutes, then dipped into a bath containing an aqueous anionic natural rubber latex emulsion.
The latex bath has a total solids content preferably about 25 to 35%, most preferably 30%, a temperature of preferably about 75 to 90F., most preferably B2F., and a pH about 9.5 to 10.6, most preferably, 10.1. The mold remains in the bath preferably about 20 to 30 seconds, most preferably 25 seconds, and is then removed, and preferably a minimum of 25 seconds is allowed for the latex film to gel. This forms the substrate layer.
The mold with the substrate layer on its surface is now O dipped into a second bath containing an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide. The total solids content of the bath is preferably about 13 to 15%, most preferably 14~, at a t~mperature preferably about 75 to 90F, :5 most preferably 82, and a pH preferably about 7 to 10, most preferably 9. The proportions in parts per hundred of the components of the bath are anionic natural rubber latex, preferably 16 to 13, most preferably 17, polyurethane latex, preferably 11 to 13, most preferably 12, poly(acrylamide/acrylic .o acid) ~10% carboxylic), preferably 0.35 to 0.43, most preferably 0.39, polyethylene oxide, preferably 0.26 to 0.32, most preferably 0.29, and water, preferably 69 to 71, most preferably 70. The mold is in the bath preferably about 25 to 45 seconds, most preferably 36, is then removed from the bath and dried, P-227~ -6- 2~97~
preferably about 160 ~o 200F., most preferably, 180~F., preferably about 160 to 180 seconds, most preferably 180 seconds. This forms the intermediate layer.
Following the formation of the intermedia-te layer over the substrate layer on the surface of the mold, the mold with the layers on its surface is spray washed, preferably about 10 to 20 minutes, most preferably 15 minutes, preferably with 120 to 150F., most preferably 130F., wate~r, then air dried preferably about 1 to 3 minutes, most preferably 2.5 minutes, preferably about 200F.
After drying, the washed and dried mold wi-th the layers on its surface has a wearer contacting layer applied over the intermediate layer by dipping the mold into a third bath containing an aqueous emulsion of acryl-ic copolymer and fluorocarbon telomer resin. The bath has a total solids content preferably about 2 to 3%, most preferably 2.5%, and a composition in parts per hundred of acrylic copolymer preferably about 1.41 to 1.88, most preferably 1.65, fluorocarbon telomer resin preferably about 34 to 38, most preferably 36, and water, preferably about 60 to 65, most preferably 62.35. The bath has a pH preferably about 6.5 to 9, most preferably 7.3. After dipping, the mold remains in the bath preferably 25 to 45 seconds, most preferably 36 seconds, then is withdrawn. The mold with the layers on its surface is then dried and cured pre~erably about 40 to 50 minutes, most preferably 44 minutes, preferably about 215 to 235F, most preferably 225F. This drying and curing step causes the layers to form a unitary structure and completes the formation of a glove.
The gloves are then stripped from the molds by everting them, having the effect of placing the last formed wearer layer on the inside. Preferably, the gloves are further treated by tumbling with a lubricant, preferably lanolin alkoxy ether, lanolin oil alkoxy ether, fluorocarbon telomer, silicone and the like, most preferably polydimethylsiloxane, preferably about 12 P-227 l 2~7 ~
7_ to 18 minu-tes, most preferably 15 minutes, preferably at 140 to 160F., most preferably 150F. to apply a coating o~ the lubricant to the surface.
Following the silicone treatment, the gloves are preferably water washed and subjected to a wet autoclaving cycle, preferably for 12 to 18 minutes, most preferably 15 minutes, pre~erably with a peak temperature about 200 to 301)F., most prefQrably 250F., then tumble dried preferably about 20 to 30 minutes about lgO to 160 F, most preferably 30 minutes and 150F.
~ atural rubber latex is known to have a protein component, which is believed to be responsible for some allergic reactions to articles formed from natural rubber. The water washing and wet autoclaving steps followed by drying produce a signi~icant reduction in the protein component as well as suhstantially j reducing any other water extractable allergenic moieties present compared to gloves not so treated and other commercial surgeon's gloves. The protein content was determined by the Bradford test, a widely used method for protein quantitation. There are man~
reports in the recent literature attributing allergic reactions, and, in some cases, anaphylaxis, to the proteins present in natural rubber latex. The instant invention's wet autoclaving step is believed to substantially remove and denature these proteins. ~ comparison using the Bradford test for protein level was made between gloves of the instant invention and known commercially available gloves intended for similar applications.
Protein Content (ug/g of glove~
Glove 5.7 Instant Invention 117.0 Surgikos MicroTouch 85.1 Baxter Triflex 0 The ability of a material to cause irritation has historically been measured by the degree of irritation to rabbit :.
:
--8- 2~
eyes. Recent efforts -to reduce the use of animals for this type of testing has led to the development of in vitro bacteria based tests. A test which has shown good correlation to the ln vivo rabbit eye test for irritation potential is the l~ninescent bacterial toxicity test, providecl under the trade name of Microtox. As shown in the table, the effective concentration (EC50) is the weight of glove mat:erial in milligrams per 1000 milliliters of extraction medium required to reduce the light output of luminescent bacteria by 50%. The larger the number, the less cytotoxic the material. A comparison using the Mic~otox test between gloves of the instant invention and gloves produced under United States Patent ~,575,476 shows that the irritation potential of the instant invention is significantly less.
~ 5 Bioluminescence (EC50) Glove : 37,000 Instant Invention 2,568 U.S. 4,575,476 Gloves manufactured according to the above described method are substantially wet hand and dry hand donnable when compared to ` o powdered natural rubber latex gloves of e~uivalent thickness and design. The intermediate layer and the wearer contacting layer applied to a natural rubber substrate can be used to impart a wet-slip and a dry-slip property to articles other than gloves as desired. When the coating layers are coupled with the water washing and wet autoclaving process steps, the detectable protein level from the natural rubber may be substantially reduced.
Further, the concentration of any other water extractable moieties having allergenic potential present in the article may be substantially reduced.
o The use of rubber gloves in medical practice has taken on added importance with the concern about Human I~nunodeficiency Virus (HIV). The strength of a glove is an important consideration to users. The instant invention of a multi-layer .
~ . ~
P--227~ ~9~
glove surprisirlgly provides a statistically significantly higher tensile strength and tear s-trength compared -to gloves manufactured according to the United States Patent No.
polyhydroxye-thyl acrylate or methacrylate and copolymers of these with each other or with acrylic or methacrylic acid, or with 2-ethylhe~yl acrylate or a ternary copolymer of 2-hydroxyethyl methacrylate, me-thacrylic acid and 2-ethylhexyl acrylate.
Gloves prepared according to the teaching of Podell et al.
can be shown to have less mechanical streng-th and reduced resistance to accelerated aging after sterilization compared to conventional powdered latex gloves. Under conditions of mechanical stress, such as extreme elongation as could occur during donning, they may partially delaminate and los0 particles from the hydrogel coating. Further, they tend to be some wha-t thicker than many powdered latex gloves thereby adversely affecting tactile sensitivity.
Summary of the Invention A multi layer flexible article includes a first layer formed from natural rubber. A second layer is formed from natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethylene oxide. A third layer is formed of acrylic copolymer and fluorocarbon telomer resin.
The article preferably may be a multi-layer surgeon's glove formed by dipping a hand shaped mold form in a series of baths.
The preferred gloves are wet hand and dry hand donnable without the need for powder, and have greater strength compared to existing gloves of similar thickness. The structure of the gloves substantially reduces the incidence of air pinhole defects in manufacture of the gloves when compared to natural rubber latex gloves of similar thickness.
A method for manufacturing multi-layer articles, preferably gloves, includes dipping a hand shaped mold form in a series of baths to form on the surface of the mold, a patient contacting first layer of natural rubber, a wearer contacting layer of acrylic copolymer and fluorocarbon telomer and, intermediate to the wearer and patient contacting layers, a layer including ~ . .
`: :
! " ' .
P--227~ 2~9~
natural rubber, polyurethane, poly(acrylamicle/acrylic acid) and polyethylene oxide. The layers are washed, dried and cured to form a unitary structure, then the st:ructure is everted as it is removed from the mold as a finished glove. The glove preferably then has a coating of lubricant applied to the surface, preferably followed by water washing, wet autoclaving and drying.
Detailed Description In accordance with the present invention, a preferred embodiment is a surgeon's glove formed on the surface of a mold.
The manufacture begins with a surface of a cleaned and coagulant treated mold form which is coated by dipping the mold in a bath containing a natural latex rubber emulsion.
The glove molds are individual for the right and left hands. The molds are made in a variety of si~es and shapes corresponding to the various hand sizes for which the gloves are intended. The molds are preferably made of ceramic, most preferably porcelain, bisque or glazed, but other materials such as stainless steel, glass, hard woods and plastic may also be used.
Suitable coagulants include, but are not limited to, calcium nitrate, calcium chloride, acetic acid, magnesium acetate, and the like. A bath with an aqueous solution of about 20 to 25%, preferably 22.5%, calcium chloride with about 0.1 to 0.2% octoxynol, preerably 0.15%, is preferred for coating the i molds with coagulant.
When the mold is dipped in the latex bath, the latex forms a patient contacting film on the surface of the coagulant coated mold which serves as a substrate for subsequent layers. The thickness of the substrate film and the subsequently applied layers is generally governed by the solids content of the emulsions, the quantity of the coagulant deposited on the mold, the temperature of the mold and the residence time of the mold in the baths.
P-227~ 2~
In a preferred embodiment, where the substra~e is formed from natural rubber latex, the porcelain molds are cleaned in a bath with aqueous sodium hypochlori-te of concentration about 2.5 to 5%, preferably 3.0%, then rinsed with 120 to 150F., preferably 135~F., water and allowed to drain. The rinsed and drained molds are then dipped in the calcium chloride coagulant bath with a temperature preferably about 110 to 130F., most preferably 120F. The molds with the coagulant on their surace are dried at about 210 to 270F. for about 8 to 10 mi.nutes, preferably 250 F. for 8.5 minutes, then dipped into a bath containing an aqueous anionic natural rubber latex emulsion.
The latex bath has a total solids content preferably about 25 to 35%, most preferably 30%, a temperature of preferably about 75 to 90F., most preferably B2F., and a pH about 9.5 to 10.6, most preferably, 10.1. The mold remains in the bath preferably about 20 to 30 seconds, most preferably 25 seconds, and is then removed, and preferably a minimum of 25 seconds is allowed for the latex film to gel. This forms the substrate layer.
The mold with the substrate layer on its surface is now O dipped into a second bath containing an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide. The total solids content of the bath is preferably about 13 to 15%, most preferably 14~, at a t~mperature preferably about 75 to 90F, :5 most preferably 82, and a pH preferably about 7 to 10, most preferably 9. The proportions in parts per hundred of the components of the bath are anionic natural rubber latex, preferably 16 to 13, most preferably 17, polyurethane latex, preferably 11 to 13, most preferably 12, poly(acrylamide/acrylic .o acid) ~10% carboxylic), preferably 0.35 to 0.43, most preferably 0.39, polyethylene oxide, preferably 0.26 to 0.32, most preferably 0.29, and water, preferably 69 to 71, most preferably 70. The mold is in the bath preferably about 25 to 45 seconds, most preferably 36, is then removed from the bath and dried, P-227~ -6- 2~97~
preferably about 160 ~o 200F., most preferably, 180~F., preferably about 160 to 180 seconds, most preferably 180 seconds. This forms the intermediate layer.
Following the formation of the intermedia-te layer over the substrate layer on the surface of the mold, the mold with the layers on its surface is spray washed, preferably about 10 to 20 minutes, most preferably 15 minutes, preferably with 120 to 150F., most preferably 130F., wate~r, then air dried preferably about 1 to 3 minutes, most preferably 2.5 minutes, preferably about 200F.
After drying, the washed and dried mold wi-th the layers on its surface has a wearer contacting layer applied over the intermediate layer by dipping the mold into a third bath containing an aqueous emulsion of acryl-ic copolymer and fluorocarbon telomer resin. The bath has a total solids content preferably about 2 to 3%, most preferably 2.5%, and a composition in parts per hundred of acrylic copolymer preferably about 1.41 to 1.88, most preferably 1.65, fluorocarbon telomer resin preferably about 34 to 38, most preferably 36, and water, preferably about 60 to 65, most preferably 62.35. The bath has a pH preferably about 6.5 to 9, most preferably 7.3. After dipping, the mold remains in the bath preferably 25 to 45 seconds, most preferably 36 seconds, then is withdrawn. The mold with the layers on its surface is then dried and cured pre~erably about 40 to 50 minutes, most preferably 44 minutes, preferably about 215 to 235F, most preferably 225F. This drying and curing step causes the layers to form a unitary structure and completes the formation of a glove.
The gloves are then stripped from the molds by everting them, having the effect of placing the last formed wearer layer on the inside. Preferably, the gloves are further treated by tumbling with a lubricant, preferably lanolin alkoxy ether, lanolin oil alkoxy ether, fluorocarbon telomer, silicone and the like, most preferably polydimethylsiloxane, preferably about 12 P-227 l 2~7 ~
7_ to 18 minu-tes, most preferably 15 minutes, preferably at 140 to 160F., most preferably 150F. to apply a coating o~ the lubricant to the surface.
Following the silicone treatment, the gloves are preferably water washed and subjected to a wet autoclaving cycle, preferably for 12 to 18 minutes, most preferably 15 minutes, pre~erably with a peak temperature about 200 to 301)F., most prefQrably 250F., then tumble dried preferably about 20 to 30 minutes about lgO to 160 F, most preferably 30 minutes and 150F.
~ atural rubber latex is known to have a protein component, which is believed to be responsible for some allergic reactions to articles formed from natural rubber. The water washing and wet autoclaving steps followed by drying produce a signi~icant reduction in the protein component as well as suhstantially j reducing any other water extractable allergenic moieties present compared to gloves not so treated and other commercial surgeon's gloves. The protein content was determined by the Bradford test, a widely used method for protein quantitation. There are man~
reports in the recent literature attributing allergic reactions, and, in some cases, anaphylaxis, to the proteins present in natural rubber latex. The instant invention's wet autoclaving step is believed to substantially remove and denature these proteins. ~ comparison using the Bradford test for protein level was made between gloves of the instant invention and known commercially available gloves intended for similar applications.
Protein Content (ug/g of glove~
Glove 5.7 Instant Invention 117.0 Surgikos MicroTouch 85.1 Baxter Triflex 0 The ability of a material to cause irritation has historically been measured by the degree of irritation to rabbit :.
:
--8- 2~
eyes. Recent efforts -to reduce the use of animals for this type of testing has led to the development of in vitro bacteria based tests. A test which has shown good correlation to the ln vivo rabbit eye test for irritation potential is the l~ninescent bacterial toxicity test, providecl under the trade name of Microtox. As shown in the table, the effective concentration (EC50) is the weight of glove mat:erial in milligrams per 1000 milliliters of extraction medium required to reduce the light output of luminescent bacteria by 50%. The larger the number, the less cytotoxic the material. A comparison using the Mic~otox test between gloves of the instant invention and gloves produced under United States Patent ~,575,476 shows that the irritation potential of the instant invention is significantly less.
~ 5 Bioluminescence (EC50) Glove : 37,000 Instant Invention 2,568 U.S. 4,575,476 Gloves manufactured according to the above described method are substantially wet hand and dry hand donnable when compared to ` o powdered natural rubber latex gloves of e~uivalent thickness and design. The intermediate layer and the wearer contacting layer applied to a natural rubber substrate can be used to impart a wet-slip and a dry-slip property to articles other than gloves as desired. When the coating layers are coupled with the water washing and wet autoclaving process steps, the detectable protein level from the natural rubber may be substantially reduced.
Further, the concentration of any other water extractable moieties having allergenic potential present in the article may be substantially reduced.
o The use of rubber gloves in medical practice has taken on added importance with the concern about Human I~nunodeficiency Virus (HIV). The strength of a glove is an important consideration to users. The instant invention of a multi-layer .
~ . ~
P--227~ ~9~
glove surprisirlgly provides a statistically significantly higher tensile strength and tear s-trength compared -to gloves manufactured according to the United States Patent No.
4,575,476. This improved strength is particularly surprising because the gloves of the instant invention are stronger even when their thickness is less than those produced under the U.S. l~
4,575,476, a widely accepted powder-free glove. A comparison of physical properties is presented below using 30 samples for the instant invention and 20 samples of gloves produced under U.S.
! 4,575 ~76. The test values and standard deviation for the values are shown.
Comparison of Physical Properties (~STM D3577-88, D412, D624) Instant Invention US 4,575,476 15 Tensile, PSI 4301 (240) 3730 (407) : Tear, PLI346 ( 44) 257 ( 393 % Elongation 903 ( 42) 898 ( 33) Modulus at 500% Elongation, PSI 548 ( 24) 425 ( 43) . 20 Thickness (Mils) Finger 8.2 10.9 Palm 8.7 9.7 Cuff 8.4 9.3 The property of high strength coupled with reduced 25 thickness resulted in the glove being rated acceptable or better for tactile sensitivity by 91% of users in a controlled use multi-site study in comparison to other premium quality surgical gloves, both powdered and powder-free. The gloves manufactured : according to the instant invention preferably have a patient 30 contacting layer about 0.05 to 0.45 mm thick, more preferably 0.15 to 0.30 mm, an intermediate layer about 0.005 to 0.20 mm i .
' - , P-227~ 2~97 ~g -thick, more preferably 0.013 to 0.05mm and a wearer contacting layer about 0.0005 to 0.05 mm thick, more pre~erably 0.001 to 0.0~5mm.
Another benefit of the inslant invention is a reduced incidence of the "air pinhole" defect experienced in glove manufacture. In a well-run glove manufacturing operation, it is generally recognized that there is some running level of various defects. A defect level of abou-t four per one thousand gloves has historically been seen for the "air pinhole" defect for natural rubber latex gloves. Most improvements to production processes are in the low percentage ranges. In the case of the instant invention, a substantial reduction of the "air pinhole"
defect is achieved. In producin~ the instant invention a reduction in the occurrence of the "air pinholè" defect to below one in one thousand gloves may be achieved, thereby greatly increasing the yield for the process. It is believed that the application of the intermediate layer present in the instant multi-layer glove over the natural rubber substrate occludes many of the "air pinholes" present in the natural rubber layer, thereby reducing the occurrence of the "air pinhole" defect.
A preferred method for manufacture of gloves of the present invention is shown as an example. It should be recognized that the components and the parameters presented here are to be considered exemplary of the principles of the invention and are not intended to limit the invention to those components and parameters illustrated. The scope of the invention will be me.asured by the appended claims and their equivalents.
Example Gloves of the present invention were formed by executing the following steps:
P-2~7 1) Cleaned molds by dippinq in an aqueous NaOC1 (3.0%) bath, removed and rinsed with 135F. water;
2) Applied coagulant to molds by dipping in an a~ueous bath, removed and air dried (8.5 min., 250F.) coaqulant bath composition and conditions Parts per hundred w/w calcium chloride 22.5 Triton X-100(Rohm and Haas)0.15 water 77.35 temperature 120F.;
3) Applied aqueous natural rubber latex to molds (substrate) by dipping in a bath for 30 seconds;
latex bath cQmE~_ition and conditions Temperature 82F.
pH 10.1 latex solids = 30%;
~) Removed from latex bath and allowed to gel for 30 seconds;
4,575,476, a widely accepted powder-free glove. A comparison of physical properties is presented below using 30 samples for the instant invention and 20 samples of gloves produced under U.S.
! 4,575 ~76. The test values and standard deviation for the values are shown.
Comparison of Physical Properties (~STM D3577-88, D412, D624) Instant Invention US 4,575,476 15 Tensile, PSI 4301 (240) 3730 (407) : Tear, PLI346 ( 44) 257 ( 393 % Elongation 903 ( 42) 898 ( 33) Modulus at 500% Elongation, PSI 548 ( 24) 425 ( 43) . 20 Thickness (Mils) Finger 8.2 10.9 Palm 8.7 9.7 Cuff 8.4 9.3 The property of high strength coupled with reduced 25 thickness resulted in the glove being rated acceptable or better for tactile sensitivity by 91% of users in a controlled use multi-site study in comparison to other premium quality surgical gloves, both powdered and powder-free. The gloves manufactured : according to the instant invention preferably have a patient 30 contacting layer about 0.05 to 0.45 mm thick, more preferably 0.15 to 0.30 mm, an intermediate layer about 0.005 to 0.20 mm i .
' - , P-227~ 2~97 ~g -thick, more preferably 0.013 to 0.05mm and a wearer contacting layer about 0.0005 to 0.05 mm thick, more pre~erably 0.001 to 0.0~5mm.
Another benefit of the inslant invention is a reduced incidence of the "air pinhole" defect experienced in glove manufacture. In a well-run glove manufacturing operation, it is generally recognized that there is some running level of various defects. A defect level of abou-t four per one thousand gloves has historically been seen for the "air pinhole" defect for natural rubber latex gloves. Most improvements to production processes are in the low percentage ranges. In the case of the instant invention, a substantial reduction of the "air pinhole"
defect is achieved. In producin~ the instant invention a reduction in the occurrence of the "air pinholè" defect to below one in one thousand gloves may be achieved, thereby greatly increasing the yield for the process. It is believed that the application of the intermediate layer present in the instant multi-layer glove over the natural rubber substrate occludes many of the "air pinholes" present in the natural rubber layer, thereby reducing the occurrence of the "air pinhole" defect.
A preferred method for manufacture of gloves of the present invention is shown as an example. It should be recognized that the components and the parameters presented here are to be considered exemplary of the principles of the invention and are not intended to limit the invention to those components and parameters illustrated. The scope of the invention will be me.asured by the appended claims and their equivalents.
Example Gloves of the present invention were formed by executing the following steps:
P-2~7 1) Cleaned molds by dippinq in an aqueous NaOC1 (3.0%) bath, removed and rinsed with 135F. water;
2) Applied coagulant to molds by dipping in an a~ueous bath, removed and air dried (8.5 min., 250F.) coaqulant bath composition and conditions Parts per hundred w/w calcium chloride 22.5 Triton X-100(Rohm and Haas)0.15 water 77.35 temperature 120F.;
3) Applied aqueous natural rubber latex to molds (substrate) by dipping in a bath for 30 seconds;
latex bath cQmE~_ition and conditions Temperature 82F.
pH 10.1 latex solids = 30%;
~) Removed from latex bath and allowed to gel for 30 seconds;
5) Applied intermediate layer over substrate by dipping molds in intermediate bath for 36 seconds;
0 intermediate bath composition and conditions Parts Per Hundred w/w Natural rubber latex (56% solids~ 17.0 Polyurethane latex (Impranil DLN, Mobay) 12.0 Poly(acrylamide/acrylic acid sodium salt), 10% Carboxyl;
(Polyscience 200,000 M.W.) 0.39 ; Polyethylene oxide (Polyox N-10 Union Carbide) 0.29 Water 70 Temperature 82 F.
pH=9 o total solids = 14%;
.
~ 6) Removed from intermediate bath and dried intermediate layer ., :, .~, ~ , ~ , '' for 180 seconds a-t 200 F.;
7) Spray washed wi-th water or 15 minutes at 130F.;
8) Dried for 2.5 minutes at 200F.;
9) Applied wearer side coating by dipping molds in wearer side bath for 35 seconds wearer side bath composition and conditions Parts per hundred w/w Acrylic copolymer (Rhoplex HG-74; Rohm and Haas, 42.5%) 1.65 Fluorocarbon telomer resin (McLube 1829; McGee Ind., 5%)36.0 Water 62.35 Total solids 2.5%
~ pH =7.3 -~ 5 Temperature 85F.;
10) Air dried and cured on molds;
Time = 44 minutes Temperature 225F.;
11) Gloves were removed from mold by everting;
12) Gloves were tumbled with silicone lubricant (polydimethyl siloxane, G.E. SM-2140), 15 minutes at 150F.;
13) Gloves were water washed (5 min. at 180F.) and wet autoclaved for a 15 minute cycle with a peak temperature at 250 F.; and ; 5 14) Gloves were tumbled dry in 30 minutes at 150F.
,.., .. ~
.
.
p-2274 20~7 ~
The gloves were subsequently sorted into pairs comprising a riyht hand and a left hand. A microorganism resistant package was formed from sealable paper laminate, and one pair of gloves was placed into each package. The package was then sealed and placed in a gamma radiation chamber for sterilization. Alternatively, packaging could be formed from non-woven, formed trays or the like, and sterilization could be conducted by steam, ethylene oxide or electron beam.
The process of applying a second layer and third layer, O described above as intermediate and wearer contacting layers, has been shown to have utility in cases where the ~irst layer is a material other than a film of natural rubber latex. ~rticles such as vinyl examination gloves formed from plastisol Polyvinylchloride (PVC) have shown benefits in powder-free donnability and in strength when coated with the intermediate and wearer contacting layers as described in the above example for natural rubber latex substrates. Additionally, the plastisol PVC
gloves have also successfully been coated with just the wearer contacting layer directly by omitting the intermediate layer, o thereby acquiring powder-free donnability. Other substrate films and flexible articles made from materials such as polyurethanes, polychloroprene, styrene/butadiene copolymer, nitrile latex and the like may benefit from the wet-slip and dry-slip properties imparted to articles by the application of the intermediate film followed by the wearer contacting coating. These articles could include other medical devices such as condoms, catheters and the like. Coatings of the wet-slip and dry-slip enhancing films followed by the above disclosed water washing and wet autoclaving process may also greatly reduce the reported incidences of anaphylaxis .reported with natural rubber enema probes and the like based on the protein reduction and cytotoxicity testing reported above.
While a number of forms of the instant invention have been . .
' :: ?
~- .
.
~, :
P-227~ 09'7~
disclosed, it wi:Ll be unders-tood that the invention may be utilized in other forms and environments, so that the purpose of the appended claims is to cover al:l such forms of devices not disclosed but which embody the invention disclosed herein.
' ~ .
0 intermediate bath composition and conditions Parts Per Hundred w/w Natural rubber latex (56% solids~ 17.0 Polyurethane latex (Impranil DLN, Mobay) 12.0 Poly(acrylamide/acrylic acid sodium salt), 10% Carboxyl;
(Polyscience 200,000 M.W.) 0.39 ; Polyethylene oxide (Polyox N-10 Union Carbide) 0.29 Water 70 Temperature 82 F.
pH=9 o total solids = 14%;
.
~ 6) Removed from intermediate bath and dried intermediate layer ., :, .~, ~ , ~ , '' for 180 seconds a-t 200 F.;
7) Spray washed wi-th water or 15 minutes at 130F.;
8) Dried for 2.5 minutes at 200F.;
9) Applied wearer side coating by dipping molds in wearer side bath for 35 seconds wearer side bath composition and conditions Parts per hundred w/w Acrylic copolymer (Rhoplex HG-74; Rohm and Haas, 42.5%) 1.65 Fluorocarbon telomer resin (McLube 1829; McGee Ind., 5%)36.0 Water 62.35 Total solids 2.5%
~ pH =7.3 -~ 5 Temperature 85F.;
10) Air dried and cured on molds;
Time = 44 minutes Temperature 225F.;
11) Gloves were removed from mold by everting;
12) Gloves were tumbled with silicone lubricant (polydimethyl siloxane, G.E. SM-2140), 15 minutes at 150F.;
13) Gloves were water washed (5 min. at 180F.) and wet autoclaved for a 15 minute cycle with a peak temperature at 250 F.; and ; 5 14) Gloves were tumbled dry in 30 minutes at 150F.
,.., .. ~
.
.
p-2274 20~7 ~
The gloves were subsequently sorted into pairs comprising a riyht hand and a left hand. A microorganism resistant package was formed from sealable paper laminate, and one pair of gloves was placed into each package. The package was then sealed and placed in a gamma radiation chamber for sterilization. Alternatively, packaging could be formed from non-woven, formed trays or the like, and sterilization could be conducted by steam, ethylene oxide or electron beam.
The process of applying a second layer and third layer, O described above as intermediate and wearer contacting layers, has been shown to have utility in cases where the ~irst layer is a material other than a film of natural rubber latex. ~rticles such as vinyl examination gloves formed from plastisol Polyvinylchloride (PVC) have shown benefits in powder-free donnability and in strength when coated with the intermediate and wearer contacting layers as described in the above example for natural rubber latex substrates. Additionally, the plastisol PVC
gloves have also successfully been coated with just the wearer contacting layer directly by omitting the intermediate layer, o thereby acquiring powder-free donnability. Other substrate films and flexible articles made from materials such as polyurethanes, polychloroprene, styrene/butadiene copolymer, nitrile latex and the like may benefit from the wet-slip and dry-slip properties imparted to articles by the application of the intermediate film followed by the wearer contacting coating. These articles could include other medical devices such as condoms, catheters and the like. Coatings of the wet-slip and dry-slip enhancing films followed by the above disclosed water washing and wet autoclaving process may also greatly reduce the reported incidences of anaphylaxis .reported with natural rubber enema probes and the like based on the protein reduction and cytotoxicity testing reported above.
While a number of forms of the instant invention have been . .
' :: ?
~- .
.
~, :
P-227~ 09'7~
disclosed, it wi:Ll be unders-tood that the invention may be utilized in other forms and environments, so that the purpose of the appended claims is to cover al:l such forms of devices not disclosed but which embody the invention disclosed herein.
' ~ .
Claims (23)
1. A flexible article comprising:
a first layer comprising natural rubber;
a second layer comprising natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethlyene oxide; and a third layer comprising an acrylic copolymer and a fluorocarbon telomer resin.
a first layer comprising natural rubber;
a second layer comprising natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethlyene oxide; and a third layer comprising an acrylic copolymer and a fluorocarbon telomer resin.
2. The article of claim 1 having an exposed surface on said first layer and an exposed surface on said third layer and at least one of said surfaces further having a coating of lubricant.
3. The article of claim 2 wherein said lubricant is selected from the group consisting of silicone, fluorocarbon telomer, lanolin oil alkoxy ethers and lanolin alkoxy ethers.
4. A multi-layer glove for use in medical procedures comprising:
a patient contacting layer formed as a film from an aqueous natural rubber latex emulsion;
a wearer contacting layer formed as a film from an aqueous emulsion comprising an acrylic copolymer and a fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, formed as a film from an aqueous emulsion comprising natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide.
a patient contacting layer formed as a film from an aqueous natural rubber latex emulsion;
a wearer contacting layer formed as a film from an aqueous emulsion comprising an acrylic copolymer and a fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, formed as a film from an aqueous emulsion comprising natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide.
5. The glove of claim 4 having an inner surface of said wearer contacting layer and an outer surface of said patient contacting layer and at least one of said surfaces having a coating of a lubricant.
6. The glove of claim 5 wherein said lubricant is selected from the group consisting of silicone, fluorocarbon telomer, lanolin oil alkoxy ethers and lanolin alkoxy ethers.
7. The glove of claim 4 wherein said patient contacting layer is from 0.05 to 0.45 mm thick, said intermediate layer is from 0.005 to 0.20 mm thick and said wearer contacting layer is from 0.0005 to 0.05 mm thick.
8. A process for making a flexible article comprising:
forming a first layer from an aqueous emulsion comprising natural rubber latex;
forming a second layer from an aqueous emulsion comprising natural rubber latex, polyurethane, poly-(acrylamide/acrylic acid) and polyethylene oxide; and forming a third layer from an aqueous emulsion comprising acrylic copolymer and fluorocarbon telomer resin.
forming a first layer from an aqueous emulsion comprising natural rubber latex;
forming a second layer from an aqueous emulsion comprising natural rubber latex, polyurethane, poly-(acrylamide/acrylic acid) and polyethylene oxide; and forming a third layer from an aqueous emulsion comprising acrylic copolymer and fluorocarbon telomer resin.
9. The process of claim 8 wherein said aqueous emulsion for forming said first layer is a bath having from 25 to 35% total solids content and a pH from 9 to 11 comprising an anionic emulsion of natural rubber latex.
10. The process of claim 8 wherein said aqueous emulsion for forming said second layer is a bath having from 10 to 20%
total solids content and a pH from 7 to 10 comprising an anionic emulsion of natural rubber latex, and anionic emulsion of an aliphatic polyester polyurethane, a sodium salt of poly(acrylamide/acrylic acid) and polyethylene oxide.
total solids content and a pH from 7 to 10 comprising an anionic emulsion of natural rubber latex, and anionic emulsion of an aliphatic polyester polyurethane, a sodium salt of poly(acrylamide/acrylic acid) and polyethylene oxide.
11. The process of claim 8 wherein said aqueous emulsion for forming said third layer is a bath having from 1.5 to 4% total a solids content and a pH from 7 to 10 comprising an aqueous emulsion of acrylic copolymer and fluorocarbon telomer resin.
12. The process of claim 8 further including applying a lubricant coating selected from the group consisting of silicone, fluorocarbon telomer, lanolin oil alkoxy ethers and lanolin alkoxy ethers to at least one of a surface of said first layer and a surface of said third layer.
13. The process of claim 8 further including water washing and autoclaving said article.
14. The process of claim 13 wherein said water washing and autoclaving comprises a water wash for from 5 to 10 minutes at from 150 to 200°F and a wet autoclaving cycle for from 10 to 20 minutes with a peak temperature from 180 to 280°F which serves to substantially denature and extract proteins found in natural rubber latex and substantially remove water extractable allergenic moieties, thereby rendering said article substantially hypoallergenic compared to articles not so treated.
15. A method for making a multi-layer glove for use in medical procedures comprising:
dipping a cleaned and coagulant coated hand mold having a surface in a first bath comprising an anionic emulsion of aqueous natural rubber latex;
forming a first film of said latex on said surface;
removing said mold having said film from said first bath;
dipping said mold having said first film in a second bath comprising an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide;
forming a second film from said emulsion of said second bath over said first film;
removing said mold having said second film over said first film from said second bath;
dipping said mold having said first film and said second film into a third bath containing an aqueous emulsion of an acrylic copolymer and a fluorocarbon telomer resin;
forming a third film over said second film and said first film from said third bath emulsion;
removing said mold having said third film over said second film and said first film from said third bath;
drying and curing said films on said mold to form a multi-layer unitary structure having a surface for contacting a wearer on said form;
stripping and everting said unitary structure from said mold thereby exposing on said structure a surface for contacting a patient;
applying a coating of lubricant to at least one of said surfaces of said structure;
washing and autoclaving said structure; and tumbling dry said structure, wherein said method results in formation of a glove.
dipping a cleaned and coagulant coated hand mold having a surface in a first bath comprising an anionic emulsion of aqueous natural rubber latex;
forming a first film of said latex on said surface;
removing said mold having said film from said first bath;
dipping said mold having said first film in a second bath comprising an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide;
forming a second film from said emulsion of said second bath over said first film;
removing said mold having said second film over said first film from said second bath;
dipping said mold having said first film and said second film into a third bath containing an aqueous emulsion of an acrylic copolymer and a fluorocarbon telomer resin;
forming a third film over said second film and said first film from said third bath emulsion;
removing said mold having said third film over said second film and said first film from said third bath;
drying and curing said films on said mold to form a multi-layer unitary structure having a surface for contacting a wearer on said form;
stripping and everting said unitary structure from said mold thereby exposing on said structure a surface for contacting a patient;
applying a coating of lubricant to at least one of said surfaces of said structure;
washing and autoclaving said structure; and tumbling dry said structure, wherein said method results in formation of a glove.
16. The method of claim 15 wherein said first bath for forming said patient contacting layer is an aqueous emulsion having from 25 to 30% total solids content and a pH from 9 to 11 comprising an anionic emulsion of natural rubber latex.
17. The glove of claim 15 wherein said second bath for forming said intermediate layer is an aqueous emulsion having from 10 to 20% total solids content and a pH from 7 to 10 comprising an anionic emulsion of natural rubber latex, an anionic emulsion of an aliphatic polyester polyurethane, a sodium salt of poly(acrylamide/acrylic acid) and polyethylene oxide.
18. The glove of claim 15 wherein said third bath for forming said patient contacting layer is an aqueous emulsion having from 1.5 to 4% total solids content and pH from 7 to 10 comprising acrylic copolymer and fluorocarbon telomer resin.
19. The method of claim 15 wherein said washing and autoclaving step comprises a water wash for from 5 to 10 minutes at from 150 to 200°F and a wet autoclaving cycle for from 10 to 20 minutes with a peak temperature about 180 to 280°F which serves to substantially denature and extract proteins found in natural latex and substantially remove water extractable allergenic moieties, thereby rendering said gloves hypoallergenic compared to gloves not so treated.
20. A method for making a multi-layer glove for use in medical procedures as in claim 15, further comprising:
sorting the articles of claim 15 into units for a package;
forming a microorganism resistant package to contain said units;
placing said units in said package;
sealing said package;
subjecting said package to a sterilizing environment; and removing said package from said sterilizing environment.
sorting the articles of claim 15 into units for a package;
forming a microorganism resistant package to contain said units;
placing said units in said package;
sealing said package;
subjecting said package to a sterilizing environment; and removing said package from said sterilizing environment.
21. The method of claim 20 wherein said articles are gloves and said units are pairs comprising a right hand glove and a left hand glove.
22. A multi-layer glove for use in medical procedures comprising:
a patient contacting layer formed from a material selected from the group consisting of plastisol PVC, natural rubber latex, polyurethane latex, polychloroprene, styrene/
butadiene copolymer and nitrite latex;
a wearer contacting layer formed from an acrylic copolymer and fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, comprising natural rubber latex, polyurethane, poly(acrylamide/acrylic acid), and polyethylene oxide.
a patient contacting layer formed from a material selected from the group consisting of plastisol PVC, natural rubber latex, polyurethane latex, polychloroprene, styrene/
butadiene copolymer and nitrite latex;
a wearer contacting layer formed from an acrylic copolymer and fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, comprising natural rubber latex, polyurethane, poly(acrylamide/acrylic acid), and polyethylene oxide.
23. A flexible article comprising:
a first layer of a plastisol PVC; and a second layer of an acrylic copolymer and a fluorocarbon telomer resin.
a first layer of a plastisol PVC; and a second layer of an acrylic copolymer and a fluorocarbon telomer resin.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US89664292A | 1992-06-10 | 1992-06-10 | |
US07/896,642 | 1992-06-10 |
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CA2097408C true CA2097408C (en) | 2000-08-08 |
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Application Number | Title | Priority Date | Filing Date |
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CA 2097408 Expired - Lifetime CA2097408C (en) | 1992-06-10 | 1993-05-31 | Flexible rubber article and method of making |
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EP (1) | EP0574160B1 (en) |
JP (1) | JP2530096B2 (en) |
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CA (1) | CA2097408C (en) |
DE (1) | DE69308172D1 (en) |
FI (1) | FI932628A (en) |
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US6251210B1 (en) * | 1996-08-07 | 2001-06-26 | Hi-Tex, Inc. | Treated textile fabric |
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-
1993
- 1993-05-25 EP EP19930304045 patent/EP0574160B1/en not_active Expired - Lifetime
- 1993-05-25 DE DE69308172T patent/DE69308172D1/en not_active Expired - Lifetime
- 1993-05-28 AU AU39901/93A patent/AU3990193A/en not_active Abandoned
- 1993-05-31 CA CA 2097408 patent/CA2097408C/en not_active Expired - Lifetime
- 1993-06-09 FI FI932628A patent/FI932628A/en not_active Application Discontinuation
- 1993-06-10 JP JP13879193A patent/JP2530096B2/en not_active Expired - Fee Related
-
1994
- 1994-06-23 US US08/264,588 patent/US5545451A/en not_active Expired - Lifetime
-
1995
- 1995-05-19 US US08/445,231 patent/US5612083A/en not_active Expired - Lifetime
- 1995-05-19 US US08/445,229 patent/US5601870A/en not_active Expired - Lifetime
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JPH0670942A (en) | 1994-03-15 |
AU3990193A (en) | 1993-12-16 |
EP0574160A1 (en) | 1993-12-15 |
FI932628A (en) | 1993-12-11 |
DE69308172D1 (en) | 1997-03-27 |
CA2097408A1 (en) | 1993-12-11 |
US5545451A (en) | 1996-08-13 |
FI932628A0 (en) | 1993-06-09 |
EP0574160B1 (en) | 1997-02-19 |
US5612083A (en) | 1997-03-18 |
US5601870A (en) | 1997-02-11 |
JP2530096B2 (en) | 1996-09-04 |
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