EP1030883A1 - Articles elastomeres fabriques a partir d'un melange de chloroprene et d'acrylonitrile - Google Patents

Articles elastomeres fabriques a partir d'un melange de chloroprene et d'acrylonitrile

Info

Publication number
EP1030883A1
EP1030883A1 EP98956637A EP98956637A EP1030883A1 EP 1030883 A1 EP1030883 A1 EP 1030883A1 EP 98956637 A EP98956637 A EP 98956637A EP 98956637 A EP98956637 A EP 98956637A EP 1030883 A1 EP1030883 A1 EP 1030883A1
Authority
EP
European Patent Office
Prior art keywords
polymer
butadiene
weight
parts
acrylonitrile
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.)
Withdrawn
Application number
EP98956637A
Other languages
German (de)
English (en)
Other versions
EP1030883A4 (fr
Inventor
Nathan M. Saks
Jason A. Baker
Fortunato G. Aldape
James S. Glenn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Microflex Corp
Original Assignee
Microflex Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microflex Corp filed Critical Microflex Corp
Publication of EP1030883A1 publication Critical patent/EP1030883A1/fr
Publication of EP1030883A4 publication Critical patent/EP1030883A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C08L11/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups

Definitions

  • This invention relates to shaped elastomeric articles, in particular to gloves, condoms and breather bags, and to polymer blends and polymer blend compositions useful in the preparation of such articles.
  • Elastomeric examination and surgeon's gloves as well as condoms and breather bags, dipped products (i.e., finger cots, catheters, balloons) and cast products (i.e., tourniquets, sheeting) are currently made from several different polymers.
  • Non-natural rubber latex products have been developed to address the issues related to natural rubber latex allergy. These current materials lack the appropriate properties necessary to serve as a suitable substitute for natural rubber latex.
  • individual polymers have specific chemical compatibility problems that limit their application in broad markets including health care, laboratory, emergency medical services and food handling.
  • nitrile elastomer is a carboxylated nitrile-butadiene elastomer.
  • the material of the Tillotson glove has a relatively low resilience; when a glove made of such material is stretched, the stress (i.e., pressure or force per unit area) exerted by the material quickly drops from its initial value. In other words, the material has a high permanent set.
  • This invention provides a blend of a polychloroprene and a nitrile polymer that yields products of equivalent or similar feel and functionality compared to the common natural rubber latex glove. These products provide equal or better feel, comfort and fit than nitrile or vinyl gloves currently available.
  • the invention further provides elastomeric films and shaped articles in film form, which are obtainable from the foregoing polymer blends on vulcanization or curing. Preferred shaped articles include gloves, condoms and breather bags and other dipped products.
  • the polychloroprene and nitrile blended gloves, condoms and breathing bags of the invention are made from synthetic elastomers and are free of allergenic latex proteins. They are made using processes similar to current manufacturing processes and techniques. The products are resistant to oxygen and ozone. Such blends yield films that have greater elongation and quicker film rebound compared to the current nitrile or vinyl products available. The blend is also softer at lower temperatures compared to current nitrile products available. The blend is more gasoline and oil resistant than current polychloroprene products available. It is also less permeable to gases than current natural rubber latex products available.
  • Tactile and physical properties of elastomers and gloves of this invention are similar to those of natural rubber latex and are better than those of other latex derived synthetic elastomers.
  • Materials and articles of this invention have good chemical and puncture resistance, similar to those of other synthetic materials and better than those of natural rubber latex.
  • materials and articles of this invention have all of the benefits of synthetic materials, and articles, e.g., good chemical resistance, good puncture resistance and no known allergens, and yet feel like natural rubber latex.
  • Materials and articles such as gloves of this invention maintain a greater percentage of initial stress over time than do nitrile elastomers and articles made therefrom. In other words, they undergo less relaxation.
  • Nitrile elastomers have a high modulus and lower elasticity so that gloves made therefrom may cause hand fatigue, in contrast, gloves made from elastomers of this invention minimize hand fatigue. Nitrile elastomers also have a permanent set, so that the materials loses resiliency and elasticity the longer it is stretched. Materials of this invention are more like natural rubber latex than nitrile elastomers in this regard. Another advantage is that materials and gloves of this invention have no unpleasant odor, while nitrile gloves have an unpleasant odor which may bother both users and patients (e.g., dental patients).
  • Fig. 1 is a graph comparing relaxation of stress over time in an elastomer latex material of this invention with prior art elastomer latex materials.
  • Fig. 2 is a bar graph showing puncture resistance in an elastomer latex material of this invention and in prior art elastomer latex materials.
  • the invention comprises elastomeric articles, in particular gloves, condoms and breathing bags constructed from a polychloroprene (or chloroprene polymer) and an acrylonitrile copolymer.
  • polychloroprene or chloroprene polymer
  • chloroprene polymer an acrylonitrile copolymer.
  • polychloroprene and chloroprene polymer are used herein to denote both poly(2-chloro-1 ,3- butadiene) homopolymer and copolymers of said 2-chloro-1 ,3-butadiene with one or more additional halogenated monomers.
  • 2-chloro-1 ,3-butadiene which is also known as chloroprene
  • the acrylonitrile copolymer is preferably a carboxylated copolymer of acrylonitrile and butadiene. However, acrylonitrile- butadiene copolymers which are not carboxylated are also useful.
  • Carboxylation is obtained by copolymerization of acrylonitrile and butadiene with a small amount (typically less than 10%) of a monomer such as acrylic acid, or methacrylic acid, or an ester thereof, such as methyl methacrylate.
  • a polymer blend as herein described, together with additional ingredients will be described below, is vulcanized or cured to yield an elastomer in film form.
  • the total blended film thickness is about 0.05 - 50 mils., preferably about 0.1-20 mils.
  • the blended film is characterized as having a tensile strength of at least (i.e., equal to or greater than) 9 MPA, preferably at least 12.5 MPA, and an elongation equal to or greater than 300%, preferably at least 500%.
  • the products are further characterized as having no latex protein allergens, low modulus, high elongation, good tensile strength, high puncture resistance, good UV (ultra-violet) resistance, good chemical resistance, and good film rebound.
  • the invention also comprises compositions and blending steps useful in producing blended elastomeric products of the types described above.
  • a general formula of an unvulcanized or uncured polymer blend composition according to this invention is set forth in Table 1. Ingredients other than the polymer blend shown in Table 1 may be conventional.
  • Polymer blending takes place prior to vulcanization.
  • a dipping form of desired shape is dipped into either a single polymer blend latex bath containing a polymer blend composition as shown in Table 1 , or into two separate polymer latex dipping baths, the first containing one of the polymers of the blend (say polychloroprene copolymer), the second containing the other polymer (say the acrylonitrile copolymer).
  • the desired polymer blend is formed on the dipping form in the latter case.
  • a single bath is preferred.
  • the dipping form is dipped into a coagulant bath and dried before it is dipped into a latex bath, whether a single latex bath or two latex baths are used.
  • the latex coated dipping form may be dipped into a warm water leach bath if desired.
  • the latex coated dipping form (or former) is then heated in an oven to cure the polymer blend latex.
  • the shape of the dipping form governs the shape of the article obtained.
  • a glove-shaped dipping form is used to obtain a polymer blend latex glove.
  • a condom-shaped dipping form is used to obtain a condom
  • a breather bag-shaped dipping form is used to obtain a breather bag.
  • films of this invention can be made by casting. Known casting techniques can be used.
  • a polymer blend as shown in Table 1 above may comprise about 10 to about 90 parts by weight of polychloroprene (homopolymer or copolymer) and about 10 to 90 parts by weight of acrylonitrile copolymer as described above.
  • the invention is summarized as an elastomeric film article (such as a glove) comprising a layer of elastomeric material which is constructed of a blend of about 10-90 parts by weight polychloroprene (homopolymer or copolymer) and about 10-90 parts by weight acrylonitrile copolymer with a tensile strength greater than 9 MPA and an elongation greater than 300%.
  • Preferred tensile strength is at least 12.5 MPA
  • preferred elongation is at least 500%.
  • This layer of elastomeric material is substantially impermeable to water and water vapor, has a thickness such that it is capable of being stretched to fit securely about a human body member and to conform to the configuration of said human body member, thereby exerting an initial pressure on said human body member, and then relaxing to exert on said body member a reduced pressure, greater than 60% of said initial pressure one minute after being stretched and greater than 50% of said initial pressure ten minutes after being stretched. More particularly, this layer has a thickness from about 0.05 to about 50 mils., preferably from about 0.1 to 20 mils., and constitutes the entire thickness of the article. More preferably the blend contains about 25-75 parts by weight polychloroprene and about 25-75 parts by weight acrylonitrile butadiene.
  • the polychloroprene may comprise poly(2-chloro-1 ,3-butadiene) or a copolymer comprising 2-chloro-1 ,3-butadiene and one or more of 2,3-dichloro-1 , 3-butadiene, 2,3-dibromo-1 ,3-butadiene, 2-chloro-3-bromo-1 ,3-butadiene or 2- bromo-3-chloro-1 , 3-butadiene, or 1 , 3-butadiene.
  • the acrylonitrile copolymer comprises a carboxylated copolymer of acrylonitrile and butadiene.
  • An elastomeric glove of this invention is characterized as having no latex protein allergens, low modulus, high elongation, high puncture resistance, high cut resistance, good UV (ultra-violet) resistance, good chemical resistance, and good film rebound. Elastomeric films, condoms and breather bags possess these same properties.
  • Polymer blend elastomers of this invention also exhibit greater oil and chemical resistance (especially to oils and non-polar hydrocarbons) than natural rubber latex and better dexterity compared to nitrile.
  • elastomeric polymer blend films of this invention and articles (such as gloves) made therefrom is high stress retention (or low relaxation) when subjected to a strain (or deformation) which remains constant over time.
  • a polymer blend film or article of this invention maintains greater than 60% of its initial stress after one minute and greater than 50% after 10 minutes.
  • Fig. 1 shows stress retention (as the percentage of initial stress) as a function of time (in minutes) for a polymer blend elastomer of this invention (denoted “NeoPro" in Fig. 1 ) and prior art elastomers, i.e., nitrile, vinyl and natural rubber latex.
  • the elastomer of this invention (NeoPro) had better stress retention than either of the other synthetic polymers.
  • Only natural rubber latex exhibited better stress retention. Disadvantages of natural rubber latex, including allergenic tendencies, lower puncture resistance and lower oil resistance are well known.
  • Fig. 1 shows stress retention (as the percentage of initial stress) as a function of time (in minutes) for a polymer blend elastomer of this invention (denoted “NeoPro" in Fig. 1 ) and prior art elastomers, i.e., nitrile, vinyl and natural rubber latex.
  • the elastomer of this invention (
  • Gloves can be made as follows.
  • a latex material having the formula set forth in Table 2 is prepared.
  • the referenced Parts Per Hundred Rubber (phr) are by weight and are based on dry material. Often, the material is in liquid form at various solid percentages by weight.
  • the sulfur is a crosslinker
  • the zinc dibutyl dithiocarbamate is an accelerator
  • the zinc oxide is an accelerator and cure agent
  • the phenolic antioxidant is an antidegradant
  • the potassium hydroxide is a pH stabilizer
  • the stabilizing surfactant is a stabilizer and wetting agent
  • the paraffin wax is a softener.
  • Clean porcelain formers are dipped into a coagulant comprising a mixture of calcium salts (i.e., calcium nitrate, calcium chloride), water and non-ionic surfactant and dried. Then the formers are dipped into the latex blend (Table 2). The latex coated formers are then leached dried and cured in an oven for 20 minutes at 235 degrees Fahrenheit. After curing, the coated formers may be leached once again in hot water and then dipped in a slurry containing water and slip agent and dried. The gloves are then stripped from the formers.
  • a coagulant comprising a mixture of calcium salts (i.e., calcium nitrate, calcium chloride), water and non-ionic surfactant and dried. Then the formers are dipped into the latex blend (Table 2). The latex coated formers are then leached dried and cured in an oven for 20 minutes at 235 degrees Fahrenheit. After curing, the coated formers may be leached once again in hot
  • Neoprene 750 was obtained from DuPont Dow Elastomers L.L.C., Wilmington, Delaware.
  • Tylac 68073 was obtained from Reichold Chemicals, Inc., Reserch Triangle Park, North Carolina.

Abstract

L'invention concerne des articles élastomères profilés, par exemple des gants, des préservatifs, et des sacs respiratoires, préparés à partir d'une composition mélangée de polymères. Cette composition renferment environ entre 10 et 90 parties en poids d'un polymère de chloroprène, et environ entre 10 et 90 parties en poids d'un polymère de nitrile, sur la base de 100 parties en poids du polymère total. Une fois durci, cet article présente une épaisseur variant entre 0,05 et 50 mils, une résistance à la traction d'au moins 9 MPA, et une élongation atteignant au moins 300 %. Lorsque cet article est étiré pour venir s'ajuster sur un membre du corps humain, par exemple la main, il exerce une pression initiale avant de se relâcher de manière à exercer une pression réduite, qui atteint au moins 50 % de ladite pression initiale. Cette invention concerne également un mélange de chloroprène et de nitrile, permettant de produire des articles provoquant une sensation et une fonctionnalité équivalente ou similaire à celles d'un gant classique en latex de caoutchouc naturel. Ces articles donnent donc une sensation équivalente ou meilleure que les gants en vinyle ou en nitrile actuellement disponibles.
EP98956637A 1997-11-07 1998-11-06 Articles elastomeres fabriques a partir d'un melange de chloroprene et d'acrylonitrile Withdrawn EP1030883A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US6474297P 1997-11-07 1997-11-07
US64742P 1997-11-07
PCT/US1998/023640 WO1999024507A1 (fr) 1997-11-07 1998-11-06 Articles elastomeres fabriques a partir d'un melange de chloroprene et d'acrylonitrile

Publications (2)

Publication Number Publication Date
EP1030883A1 true EP1030883A1 (fr) 2000-08-30
EP1030883A4 EP1030883A4 (fr) 2005-09-21

Family

ID=22057996

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98956637A Withdrawn EP1030883A4 (fr) 1997-11-07 1998-11-06 Articles elastomeres fabriques a partir d'un melange de chloroprene et d'acrylonitrile

Country Status (6)

Country Link
EP (1) EP1030883A4 (fr)
JP (1) JP2001522921A (fr)
AU (1) AU741202B2 (fr)
CA (1) CA2303375A1 (fr)
ID (1) ID25890A (fr)
WO (1) WO1999024507A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6195805B1 (en) * 1998-02-27 2001-03-06 Allegiance Corporation Powder free neoprene surgical gloves
US6000061A (en) * 1998-11-18 1999-12-14 Pt. Irama Dinamika Latex Glove made from a blend of chloroprene rubber and a carboxylated synthetic butadiene rubber
US6451893B1 (en) * 2001-05-22 2002-09-17 Microflex Corporation Soft nitrile zinc oxide free medical gloves
GB0211027D0 (en) * 2002-05-14 2002-06-26 Ssl Internat Double-donnable glove
CN101796122B (zh) 2007-08-09 2013-07-31 普拉泰克斯产品有限公司 聚合物胶乳复合物
AU2009339262C1 (en) 2009-02-05 2015-08-13 Diptech Pte Limited Production of elastomeric films
RU2550827C2 (ru) * 2013-07-01 2015-05-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Чувашский государственный университет имени И.Н. Ульянова" Резиновая смесь
RU2547477C2 (ru) * 2013-07-09 2015-04-10 Федеральное государственное унитарное предприятие "Научно-производственное предприятие "Прогресс" (ФГУП "НПП "Прогресс") Маслостойкая резиновая композиция
AU2014292805C1 (en) 2013-07-16 2018-06-14 Skinprotect Corporation Sdn Bhd Elastomeric film-forming compositions and articles made from the elastomeric film
US10626283B2 (en) * 2013-11-19 2020-04-21 Ansell Limited Polymer blends of nitrile rubber and polychloroprene
EP3289012A2 (fr) * 2015-04-28 2018-03-07 Avent, Inc. Gant en caoutchouc nitrile à modificateur d'étirement
US10154699B2 (en) 2015-09-10 2018-12-18 Ansell Limited Highly chemical resistant glove
MY190526A (en) * 2016-12-30 2022-04-27 Skinprotect Corp Sdn Bhd Elastomeric film-forming compositions and associated articles and methods
CN110054819B (zh) * 2019-04-22 2021-07-27 山东津莱环海医疗科技有限公司 一种氯丁橡胶麻醉储气囊
MY196386A (en) * 2019-05-23 2023-03-28 Top Glove Int Sdn Bhd Elastomeric Article
AU2022319176A1 (en) * 2021-07-27 2024-03-07 Ansell Limited Accelerator free synthetic gloves with high tear resistance

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Publication number Priority date Publication date Assignee Title
US3823024A (en) * 1972-05-10 1974-07-09 Grace W R & Co Process for forming a strippable coating
EP0486183A1 (fr) * 1990-11-14 1992-05-20 Reichhold Chemicals, Inc. Gant en latex facile à enfiler
WO1996040306A1 (fr) * 1995-06-07 1996-12-19 Allegiance Corporation Gants de chirurgie realises a partir de copolymeres de neoprene

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US3943192A (en) * 1968-03-05 1976-03-09 Polysar Limited Elastomeric blends
US4048261A (en) * 1975-11-10 1977-09-13 The B. F. Goodrich Company Vulcanizable compositions of a halogen-containing polymer and a diene-nitrile rubber having active halogen cure sites
DE3934954A1 (de) * 1989-10-20 1991-04-25 Bayer Ag Kautschukmischungen aus polychloropren und hydriertem nitrilkautschuk

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3823024A (en) * 1972-05-10 1974-07-09 Grace W R & Co Process for forming a strippable coating
EP0486183A1 (fr) * 1990-11-14 1992-05-20 Reichhold Chemicals, Inc. Gant en latex facile à enfiler
WO1996040306A1 (fr) * 1995-06-07 1996-12-19 Allegiance Corporation Gants de chirurgie realises a partir de copolymeres de neoprene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9924507A1 *

Also Published As

Publication number Publication date
CA2303375A1 (fr) 1999-05-20
AU1311499A (en) 1999-05-31
JP2001522921A (ja) 2001-11-20
AU741202B2 (en) 2001-11-22
EP1030883A4 (fr) 2005-09-21
ID25890A (id) 2000-11-09
WO1999024507A1 (fr) 1999-05-20

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