WO2019046906A1 - Article élastomère synthétique et ses procédés de production - Google Patents

Article élastomère synthétique et ses procédés de production Download PDF

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Publication number
WO2019046906A1
WO2019046906A1 PCT/AU2018/050976 AU2018050976W WO2019046906A1 WO 2019046906 A1 WO2019046906 A1 WO 2019046906A1 AU 2018050976 W AU2018050976 W AU 2018050976W WO 2019046906 A1 WO2019046906 A1 WO 2019046906A1
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WO
WIPO (PCT)
Prior art keywords
polyol
elastomeric
article
coating
elastomeric article
Prior art date
Application number
PCT/AU2018/050976
Other languages
English (en)
Inventor
Khon Pu Foo
Chin Keong LIM
Cian Ying TUNG
Original Assignee
Skinprotect Corporation Sdn Bhd
BORHAM, Janelle
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
Priority claimed from AU2017903688A external-priority patent/AU2017903688A0/en
Application filed by Skinprotect Corporation Sdn Bhd, BORHAM, Janelle filed Critical Skinprotect Corporation Sdn Bhd
Priority to AU2018329205A priority Critical patent/AU2018329205B2/en
Priority to CN201880069538.4A priority patent/CN111542242B/zh
Publication of WO2019046906A1 publication Critical patent/WO2019046906A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/26—Crosslinking, e.g. vulcanising, of macromolecules of latex
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/26—Electrically protective, e.g. preventing static electricity or electric shock
    • A41D31/265—Electrically protective, e.g. preventing static electricity or electric shock using layered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/015—Protective gloves
    • 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
    • A61B42/10—Surgical gloves
    • 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
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0064—Producing wearing apparel
    • B29D99/0067—Gloves
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C08J2309/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials

Definitions

  • the present application relates to elastomeric articles and methods for their production.
  • the present application relates in particular to dipped elastomeric articles such as gloves, which have the ability to dissipate static charge.
  • Control of static electricity can be critical in many settings, where an undesired electrostatic discharge or spark can result in serious damage or can damage sensitive integrated circuits.
  • Gloves having electrostatic dissipative (ESD) properties are vital, especially for use in handling electronic equipment. Excessive electrostatic charge contributed by movement between two different materials causes damage of electronic components. By wearing gloves with ESD properties the possibility of static discharges occurring between the worker and other objects is reduced.
  • Gloves having ESD properties are typically produced using a conductive filler such as a carbonaceous filler (such as carbon black, carbon nanotube, graphite, graphene and the like) and/or a metallic filler (such as silver, copper, aluminium and the like).
  • a conductive filler such as a carbonaceous filler (such as carbon black, carbon nanotube, graphite, graphene and the like) and/or a metallic filler (such as silver, copper, aluminium and the like).
  • a conductive filler such as a carbonaceous filler (such as carbon black, carbon nanotube, graphite, graphene and the like) and/or a metallic filler (such as silver, copper, aluminium and the like).
  • the high loading of conductive filler that is required to produce gloves with desired ESD properties significantly increases the material cost. Further, the conductive filler is known to migrate out of the glove and into human skin, which poses a health risk due to the carcinogenic properties of carbonaceous filler.
  • ionic compounds such as lithium salts, alkali carboxylates and quarternary ammonium salts, have been used to provide ESD properties to various products.
  • ionic compounds such as lithium salts, alkali carboxylates and quarternary ammonium salts
  • the use of ionic compounds in the context of gloves to be used under clean room conditions is not appropriate as the particle content and ionic content of clean room gloves are strictly controlled.
  • the present inventors have discovered that it is possible to obtain beneficial ESD properties in an elastomeric article through the incorporation of a coating layer comprising a polyol material, or an improvement in the ESD performance without a prohibitive negative impact on the glove properties.
  • a dipped elastomeric article comprising an elastomeric film and a coating layer on a surface of the elastomeric film, the coating layer comprising a polyol material selected from the group consisting of polyols, polyol esters and polyol derivatives, wherein the elastomeric article has a surface resistivity of 10 11 ⁇ /sq or less.
  • the elastomeric article has one or more of the following properties: - a tribo-electrical charge before rub of less than 50V and after rub of less than 300V, and/or - a static decay time (from 1000V to 10V) of less than 1 second.
  • the coating layer may remain entirely on the surface of the elastomeric film or it can penetrate partially into the elastomeric film such that some coating layer remains on the surface of the elastomeric film.
  • the elastomeric film may comprise the polyol material.
  • the polyol material may be incorporated into the elastomeric film through its incorporation into a coagulant composition used in the production of the elastomeric article, or through incorporation into the liquid latex composition (the so-called “elastomeric film-forming composition") used to form the elastomeric film, or through both techniques.
  • the polyol material may be present within the elastomeric film in a distribution that is consistent with the polyol material being present in a coagulant composition used in the preparation of the elastomeric article, or in a distribution that is consistent with the incorporation of the polyol material into an elastomeric film-forming composition used in the preparation of the elastomeric film.
  • a method of manufacturing a dipped elastomeric article comprising an elastomeric film that has a surface resistivity of 10 11 ⁇ /sq or less, the method comprising:
  • step (d) applying a coating composition comprising a polyol material to a surface of the elastomeric film produced in step (c),
  • polyol material is selected from the group consisting of polyols, polyol esters and polyol derivatives.
  • the method further comprises:
  • step (i) incorporating a polyol material into the coagulant composition used in step (a), and/or (ii) incorporating a polyol material into the elastomeric film-forming composition used in step (b).
  • an elastomeric glove produced by the method described above.
  • ESD electrostatic dissipative
  • Electrostatic charge is created when materials are rubbed together and then separated, such that one material gives up electrons and the other material accumulates them. When these materials contact each other again, a static shock is created to correct the imbalance.
  • Articles having electrostatic dissipative (ESD) properties are those that reduce the build-up of static electricity and triboelectric charging.
  • the electrostatic dissipative (ESD) properties of an article may be measured by surface resistivity and/or tribo-electrical charge.
  • Surface resistivity is the resistance to a drop in voltage (or leakage current) along the surface of a material, and is measured in ⁇ (ohm) or ⁇ /sq. As the ability of a material to dissipate electric charge improves, the surface resistivity ( ⁇ /sq) will decrease. Generally, materials having electrostatic dissipative (ESD) properties will have a surface resistivity of 10 11 ⁇ /sq or less.
  • ESD electrostatic dissipative
  • surface resistivity is measured in accordance with the procedure specified in ASTM D257. It should be noted that other test techniques are available for testing surface resistivity and resistance. However, the surface resistivity measurements taken in such tests may be influenced by the conductivity of the underlying substrate when conducting the test (e.g.
  • test set by ASTM D257 is not influenced by such conditions, and is accordingly the test that is to be applied when considering the properties of articles, and comparing to the claims.
  • Tribo-electrical charging causes certain materials to become electrically charged after they come into frictional contact with another material. When the electrically charged surface of the material contacts another material that is uncharged or has a substantially different charge, an electrical discharge of the built-up static electricity may occur. Generally, materials having electrostatic dissipative (ESD) properties that will minimize static charging have a tribo-electrical charge closer to zero. Tribo-electrical charge can be measured through a number of different techniques. In the present application, the procedure used is a modified procedure based on that specified in ESD TR-03-99 of the ESD Association Standard Technical Report for the Protection of Electrostatic Discharge Susceptible Items. The modified procedure is described below in the Examples, under the heading
  • Triboelectric charge It will be appreciated that tribo-electrical charge could be determined by a different test, but this would not, of itself, avoid the scope of the present application.
  • Static decay time is the time taken for a charged plate of 1000V to dissipate to 90% to 99% of its initial charge after being touched by an ESD glove.
  • the charged plate is initially charged to 1000V, followed by a finger touching of an ESD glove on the plate for which time is recorded for the charge to dissipate to 10V.
  • the static decay can be measured in accordance with the procedure specified in FTMS-101 Method 4046, Federal Test Method Standard - Test Procedures for Packaging Material - Electrostatic Properties of Materials or ESD TR 03-99 of the ESD Association Standard Technical Report for the Protection of Electrostatic Discharge Susceptible Items.
  • FTMS-101 Method 4046 is employed.
  • articles having electrostatic dissipative (ESD) properties will have a static decay time of less than 1 second.
  • the present inventors have found that the inclusion of one or more polyol materials in a coating on a surface of an elastomeric film of a dipped elastomeric article can provide the dipped elastomeric article with a surface resistivity of 10 11 ⁇ /sq or less.
  • the elastomeric article has a surface resistivity of less than about 10 11 ⁇ /sq, about 10 10 ⁇ /sq or less, from about 10 11 ⁇ /sq to about 10 s ⁇ /sq, or from about 10 10 ⁇ /sq to about 10 7 ⁇ /sq.
  • Preferred ranges for the surface resistivity of the elastomeric articles are between 10 6 - 10 10 , 10 7 - 10 10 , 10 7 - 10 9 ⁇ /sq.
  • the present inventors have found that the inclusion of one or more polyol materials in a coating on a surface of an elastomeric film of a dipped elastomeric article can provide the elastomeric article with a tribo-electrical charge before rub of less than 50V and after rub of less than 300V.
  • the elastomeric article has a tribo-electrical charge before rub of less than 40V, less than 30V or less than 20V.
  • the after rub tribo-electrical charge value is less than 280V, less than 260V, less than 240V, less than 220V, less than 200V, less than 180V, less than 160V or less than 150V. Any of the before and after rub values indicated can be combined.
  • the present inventors have found that the inclusion of one or more polyol materials in a coating on a surface of an elastomeric film of a dipped elastomeric article can provide the elastomeric article with a static decay time (from 1000V to 10V) of less than 1 second.
  • the elastomeric article has a static decay time of less than 0.8 second, less than 0.6 second, less than 0.5 second, less than 0.2 second, less than 0.1 second, less than 0.05 second and about 0 seconds.
  • the elastomeric article having electrostatic dissipative (ESD) properties may comprise a coating layer on the outwardly-facing (or
  • the elastomeric article may have any of the surface resistivity values and tribo-electrical charge values as indicated in the preceding paragraph(s), in any combination.
  • the dipped elastomeric article having electrostatic dissipative (ESD) properties may include the polyol material within the elastomeric film, which may be by inclusion of the polyol material in the coagulant and/or in the elastomeric film-forming composition used to prepare the elastomeric article, in addition to the polyol-containing coating.
  • the elastomeric article may have a surface resistivity of 10 11 ⁇ /sq or less, from about 10 11 ⁇ /sq to about 10 s ⁇ /sq, or from about 10 10 ⁇ /sq to about 10 s ⁇ /sq.
  • the values for surface resistivity, tribo-electrical charge and static decay time in various embodiments for this form of article may be in accordance with any one or more of the values indicated above, in any combination.
  • the surface resistivity of the gloves may decrease during storage.
  • the surface resistivity of the article can decrease during storage to a constant surface resistivity of about 10 10 ⁇ /sq, 10 9 ⁇ /sq, 10 8 ⁇ /sq, 10 7 ⁇ /sq or 10 s ⁇ /sq.
  • polyol material encompasses polyols, polyol esters, and polyol derivatives.
  • Suitable polyols, polyol esters and polyol derivatives are those compounds capable of absorbing moisture from the environment in order to be dissipate static charge.
  • polyol refers to a molecule having two or more hydroxyl groups. In some embodiments, the polyol will have from 2 to 9 hydroxyl groups.
  • the polyol may be a polymeric polyol, based on a repeating sub-unit (e.g. polyethylene glycol), or the polyol may be a monomeric polyol (e.g. sorbitol).
  • the number of hydroxyl groups in the polyol may also be expressed as a hydroxyl number, which is calculated by determining the milligrams of potassium hydroxide equivalent to the hydroxyl content in one gram of polyol. The hydroxyl number can be calculated in accordance with the procedure specified in ASTM E222 and E1899.
  • the polyol will have a hydroxyl number of at least 20 mg/g and above. Preferably, the polyol will have a hydroxyl number of more than 200 mg/g, or more than 1000 mg/g. In some embodiments, the polyol comprises at least one free hydroxyl group.
  • polystyrene resin examples include polyethylene glycols (PEG), polyethylene oxides (PEO), polypropylene glycols (PPG), monomeric diols, monomeric triols, sugars, sugar alcohols, and polysaccharides.
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • monomeric diols monomeric triols
  • sugars sugar alcohols
  • polysaccharides polysaccharides.
  • Monomeric diols are molecules containing no repeating units, and two hydroxyl groups.
  • Suitable monomeric diols are those containing between 2 and 12 carbon atoms and two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, hexaethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, diethanolamine, 1 ,3-propanediol, 1 ,3- butanediol, 1 ,4-butanediol, 1 ,6-hexanediol and so forth.
  • Monomeric triols are molecules are hydrocarbon compounds containing no polymeric repeated units, and three hydroxyl groups.
  • Suitable monomeric triols are those containing between 2 and 12 carbon atoms and three hydroxyl groups, examples of which include glycerol, triethanolamine, and 1 ,2,6-Hexanetriol.
  • Sugars include the monosaccharides and disaccharides, pentoses, hexoses, and so forth, which may be naturally occurring or synthetic. Examples include sucrose, glucose, lactose, fructose, mannitose, sorbitose, and maltose.
  • Sugar alcohols are polyhydric alcohols typically derived from sugars, for example through hydrogenation of the corresponding sugar. Sugar alcohols include sorbitol, mannitol, xylitol and erythritol. Polysaccharides such as cellulose may also be used.
  • the polyol is selected from the group consisting of polyethylene glycols (PEG) with an average molecular weight of between 200 and 22,000 g/mol, about 200 to about 20,000 g/mol or about 200 to about 6000 g/mol; polyethylene oxides (PEO) with a molecular weight of between 20,000 and 10,000,000 g/mol or about 20,000 to about 100,000 g/mol; polypropylene glycols (PPG) with a molecular weight of between 300 and 4000 g/mol, about 400 to about 4000 g/mol, or about 400 to about 2000 g/mol; monomeric diols containing between 2 and 12 carbon atoms; monomeric triols containing between 2 and 12 carbon atoms; sugars and sugar alcohols.
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • polyol ester refers a compound having one or more hydroxyl functional groups and at least one ester functional group.
  • the polyol ester comprises at least one - OH group, preferably between 1 -6 -OH groups.
  • the polyol ester has a hydrophilic: lipophilic balance value (HLB value) of at least 5. In some embodiments, the polyol ester has a HLB value of 8 to 18. In some embodiments, the polyol ester is prepared by reaction of a polyol as defined above with a suitable carboxylic acid to form a polyol ester.
  • the carboxylic acid may consists of at least 4 carbon atoms, preferably a medium chain carboxylic acid with 6-12 carbons or a long chain carboxylic acid with 13-21 carbon atom.
  • the carboxylic acid may be saturated, unsaturated, aliphatic or aromatic.
  • the carboxylic acid derives from natural resources such as fatty acid from plant (palm oil, coconut oil, cocoa butter, olive oil, soy bean oil, corn oil, sunflower oil, castor oil and the like), including fatty acids from animals (such as beeswax). These may be hydrogenated or non-hydrogenated.
  • fatty acids from plants are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid and the like.
  • carboxylic acids include those derived from other organic acid such as fumic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, lactic acid, malic acid, citric acid, benzoic acid, acrylic acid, salicylic acid and the like.
  • suitable polyol esters include PEG esters (including PEG fatty acid esters and PEG glycerol fatty acid esters, such as PEG oleate, PEG cocoate, PEG stearate, PEG acrylate, PEG glycerol cocoate, PEG 40-hydrogenated castor oil), glycerol esters (including glycerol stearate, glycerol oleate, glycol acrylate, polyglycerol esters of fatty acids) and sorbitan esters (such as sorbitan laurate, sorbitan stearate, sorbitan palmitic, and including polysorbates such as Polysorbate 20 and Polysorbate 80).
  • PEG esters including PEG fatty acid esters and PEG glycerol fatty acid esters, such as PEG oleate, PEG cocoate, PEG stearate, PEG acrylate, PEG glycerol cocoate, PEG 40-hydrogenated cast
  • the polyol ester is selected from the group consisting of PEG esters where the PEG has a molecular weight of between 200 and 22,000 g/mol, PEO esters where the PEO has a molecular weight of between 20,000 and 10,000,000 g/mol, PPG esters where the PPG has a molecular weight of between 300 and 4000 g/mol, glycerol esters and sorbitan esters, wherein the polyol ester preferably has an HLB of at least 5.
  • the polyol ester is selected from the group consisting of polyethylene glycol esters, glycerol esters and sorbitan esters.
  • a "polyol derivative” refers to the product produced by reacting a polyol with a compound having functional groups such as a hydroxyl group, an alkane group, an alkene group, an ester group, an ether group, an amino group, an amide group, a carboxylate group, an aldehyde group, or a ketone group.
  • a polyol derivative may or may not include a free hydroxyl functional group, depending on whether all the hydroxyl groups in the polyol are reacted with the functional groups of the compound used to form the polyol derivative.
  • the polyol derivative contains at least one hydroxyl functional group.
  • suitable polyol derivatives include methoxypolyethylene glycol (MPEG), copolymers of ethylene oxide and propylene oxide, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • PEG ethers ethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol propoxylated ethylenediamine polyol.
  • the polyol derivative is selected from the group consisting of methoxypolyethylene glycol (MPEG) with a molecular weight between 350 and 750 g/mol, copolymers of ethylene oxide and propylene oxide with a molecular weight between 2000 and 5000 g/mol, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • PEG ethers ethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol propoxylated ethylenediamine polyol.
  • Preferred polyol derivatives are non-elastomeric polyol derivatives.
  • the polyol material is: - a polyol selected from the group consisting of: polyethylene glycols (PEG), polyethylene oxides (PEO), polypropylene glycols (PPG), monomeric diols, monomeric triols, sugars, sugar alcohols, and polysaccharides;
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • monomeric diols monomeric triols
  • sugars sugar alcohols
  • polysaccharides polysaccharides
  • PEG esters including PEG fatty acid esters and PEG glycerol fatty acid esters, such as PEG oleate, PEG cocoate, PEG stearate,
  • PEG acrylate PEG glycerol cocoate, PEG 40-hydrogenated castor oil
  • glycerol esters including glycerol stearate, glycerol oleate, glycol acrylate, polyglycerol esters of fatty acids
  • sorbitan esters such as sorbitan laurate, sorbitan stearate, sorbitan palmitic, and including polysorbates such as Polysorbate 20 and Polysorbate 80
  • a polyol derivative selected from the group consisting of: methoxypolyethylene glycol (MPEG), copolymers of ethylene oxide and propylene oxide, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • copolymers of ethylene oxide and propylene oxide glycol ethers
  • PEG ethers ethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol propoxylated ethylenediamine polyol
  • the polyol material may be selected from the group consisting of glycerine, PEG 300, PEG 400, PEG 600, PEG 1000, PEG 6000, poly glycerol fatty acid ester, sorbitol, PEG 7 glyceryl cocoate, polysorbate 20, polysorbate 80, polyether and PEG 40 hydrogenated castor oil.
  • the coating comprises two or more different polyol materials.
  • the different polyols may be of the same class (e.g. both may be monomeric diols), or they may be of different classes or subclasses. Where two or more different polyol materials are present, each of the polyol materials may be selected from the polyols, polyol esters and polyol derivatives as described above.
  • the elastomeric article may comprise two or more different polyol materials, including:
  • the coating may comprise two or more different polyol materials, including:
  • polyol material should not be interpreted as encompassing only those materials that retain two or more hydroxyl functional groups. While polyols, as defined herein, contain two or more hydroxyl functional groups, polyol esters may contain a single hydroxyl functional group, and polyol derivatives may contain no hydroxyl groups after derivatisation.
  • the dipped elastomeric articles comprise the polymeric material in a coating layer on a surface of an elastomeric film.
  • the coating layer may be formed by applying a coating composition comprising a polyol material to a surface of the elastomeric film.
  • the polyol material can be incorporated into the elastomeric article by the application of the polyol material directly (i.e. neat or unblended) or by application of a coating composition containing the polyol material.
  • the coating composition may comprise, in addition to the polyol material, a solvent and optionally one or more additives.
  • the additive may be present in an amount from 0-30% by weight of the coating composition, for example, from 0-10%, 0-20%, 0.1 -30%, 0.1 -20%, 0.1 - 10%, 1 -30%, 1 -20% or 1 -10% by weight of the coating composition.
  • the one or more additives may include a wetting agent, a thickener or a combination thereof.
  • any solvent capable of dissolving the polyol material and dispersing it across the surface of the elastomeric film before removal may be used.
  • Suitable solvents include water, ethanol, methanol, butanol, ethyl acetate, acetone, acetonitrile, dichloromethane, benzene, toluene, hexane, isopropyl alcohols and combinations thereof.
  • the solvent is water.
  • the coating composition comprises a combination of solvents, for example, water and ethanol.
  • One advantage to mixed solvent systems is that one of the solvents may have a lower boiling point and may therefore assist in faster drying times for the coating composition.
  • Suitable quick drying solvents including ethanol, methanol, acetone, ethyl acetate and combinations thereof.
  • the solvent may be present in amounts of up to 99% by weight, for example, from 10-99% by weight or 50-70% by weight based on the weight of the coating composition.
  • the solvent will be removed in a drying step after the coating composition has been applied to the surface of the elastomeric film.
  • the quick drying solvent may be present in the coating composition in an amount of up to 40% by weight, for example, from 0.01 -40% or 1-30% by weight.
  • any wetting agent able to assist spread the coating composition across the surface of the elastomeric film may be used.
  • Suitable wetting agents include non-ionic surfactants, including fluoro-surfactants and ethoxylates (e.g. fatty alcohol ethoxylates, alkylphenol ethoxylates, fatty acid ethoxylates, ethoxylated fatty esters and oils, ethoxylated amines and so on).
  • the coating composition may comprise a wetting agent in an amount of up to 1 % by weight, for example, from about 0.01 -1 % by weight or about 0.01 to about 0.5% by weight.
  • the wetting agent may assist in spreading the coating composition across the surface of the elastomeric film.
  • the coating composition may comprise one or more thickeners. If present, the thickener will remain as a component of the coating layer on the dipped elastomeric article after drying/evaporation of the solvent(s).
  • a thickener in the coating composition is that a thicker layer is formed on the elastomeric film allowing for a larger amount of coating to be applied to the surface of the film.
  • Suitable thickeners include celluloses (e.g. methylcellulose, hydroxypropyl methylcellulose, and so forth) and gelling agents (starches, gums, pectins) and the like.
  • the coating composition may comprise a thickener in an amount of up to about 5% by weight, for example, from about 0.001 -1 %, 0.1 - 2% or 0.01 -0.5% by weight.
  • the coating layer comprising the polyol material is present on an outwardly-facing ("outer" or "external") surface of the article.
  • the coating layer may be present on only the outer surface of the article, or the coating layer may be present on both the outer and inner surfaces of the article.
  • the coating may not extend across the entirety of the surface of the elastomeric film. In some embodiments, the coating extends across up to 100%, 95%, 90%, 80%, 75%, 60% 50%, or less of the surface.
  • a manufacturer of products in accordance with the present application can purchase in elastomeric articles and apply the coating composition comprising the polyol material to the articles, or the manufacturer can produce the elastomeric articles and then apply the coating composition.
  • Methods for the manufacture of elastomeric articles which may be subjected to a coating step are described herein.
  • the elastomeric articles subjected to the coating step may themselves contain a polyol material in the elastomeric film itself, or they may be polyol material-free.
  • the coating layer comprises the polyol material in an amount sufficient to provide the elastomeric article with electrostatic dissipative (ESD) properties.
  • ESD electrostatic dissipative
  • the total weight of the (dried) coating may be between 0.0001 and 80% by weight of the elastomeric article.
  • the weight percentage of the article taken up by the coating layer in the final product i.e. a dried weight
  • the weight percentage of the article taken up by the coating layer in the final product may be a minimum of 0.001 %, 0.01 %, 0.05%, 0.1 %, 0.5%, 1 %, 1 .1 %, 1 .2%, 1 .3%, 2.5%, 5%, 7.5% or 10% by weight (based on the total article weight).
  • the weight percentage of the article taken up by the coating may be less than 80%, 70%, 60%, 50%, 40%, 30%, 25%, 22.5%, 20%, 17.5%, 15%, 12.5%, 10%, 7.5%, 5%, 4% or 3% by weight of the total article weight. Any minimum and maximum can be combined to form a range, provided that the maximum is greater than the minimum, such as a range of between 0.1 % and 25%.
  • the polyol material in the coating layer constitutes about 0.001 % to 80% by weight of the total weight of the article.
  • the polyol material in the coating layer may constitute 0.001 % to 60%, 0.001 % to 40%, 0.001 % to 20%, 0.005% to 20%, 0.008% to 20%, 0.01 % to 20%, 0.005% to 10%, 0.008% to 10%, 0.01 % to 10%,
  • the polyol material in the coating layer constitutes about 0.1 to 7% by weight of the total weight of the article.
  • the total amount of polyol material in the coating layer is at least 5% by weight of the coating layer.
  • the total amount of polyol material in the coating layer is from about 5% to 100%, from about 10% to 100%, from about 20% to 100%, from about 25% to 100%, from about 30% to about 100%, from about 40% to about 100%, or from about 50% to about 100% by weight of the coating layer.
  • the weight of the article taken up by the polyol material in coating form may be a minimum of 0.001 %, 0.01 %, 0.05%, 0.1 %, 0.5%, 1 %, 2.5%, 5%, 7.5% or 10% by weight (based on the total article weight).
  • the weight percentage of the article taken up by polyol material in coating form, as a percentage of the total article weight may be less than 80%, 70%, 60%, 50%, 50%, 40%, 30%, 25%,22.5%, 20%, 17.5%, 15%, 12.5%, 10%, 7.5% or 5% by weight. Any minimum and maximum can be combined to form a range, provided that the maximum is greater than the minimum, such as a range of between 0.1 % and 25%.
  • the coating composition may be applied in a typical amount of at least 1 mg of dried polyol.
  • the glove coating composition may be applied in an amount of from about 4mg to 1000mg, equivalent to 0.1 % to 25% by weight of the total glove weight.
  • the volume of coating composition picked up by a dipped glove may be about 0.1 mL or more, preferably about 0.5 mL to about 5 mL per glove.
  • the coating layer (or polyol material coating) is preferably acrylate free.
  • the polyol material coating is preferably hydrogel free.
  • the polyol material coating is preferably silicon-free.
  • the polyol material coating is preferably phthalate-free.
  • the polyol material coating is preferably lithium-ion free.
  • the polyol material coating is preferably quaternary ammonium salt-free. Consequently, in preferred embodiments, the coating layer in the dipped elastomeric article is free of one or more, or all of the above-listed components.
  • the polyol material may be incorporated into (within) the elastomeric film of the dipped elastomeric article.
  • the polyol may be incorporated through any one of these techniques (i) or (ii), or through a combination of both. Typically, either or both of these techniques are employed together with the application of a coating comprising the polyol material to the elastomeric film; however, also provided are dipped elastomeric products absent the coating layer.
  • the polyol material is incorporated into the elastomeric article so that the polyol material is absorbed and/or embedded in the elastomeric article or within the elastomer polymer network and matrices, and does not leach out of the elastomeric article.
  • incorporation by way of addition of the polyol into the film- forming composition then incorporation by way of addition into the coagulant.
  • additional details of the methods used to incorporate the polyol material are described.
  • One technique for incorporating the polyol material into the elastomeric film is by way of including the polyol material in the latex composition (elastomeric film-forming composition) that is used to form the elastomeric article.
  • the polyol material is mixed into an elastomeric film-forming composition, and a glove-shaped former is dipped into the elastomeric film-forming composition to form a glove-shaped elastomeric film containing the polyol material.
  • the polyol material may be present as a blend with the other components of the elastomeric film-forming composition may be by way of a blend, where the polyol material remains separate from (i.e.
  • the polyol material is coupled to the elastomer-forming polymer. This may be by way of covalent bonding or ionic bonding. In another embodiment, the polyol material is associated with the elastomer- forming polymer by way of hydrogen bonding or another form of intermolecular bonding.
  • the polyol material may migrate to the glove surface upon storage, thus reducing the surface resistivity of the glove.
  • the polyol may alternatively remain throughout the elastomeric film (matrix), but at a concentration or in an amount such that the outwardly- facing surface has ESD properties.
  • the process typically involves dipping of a former (i.e. a mould) into a coagulant, followed by dipping into an elastomeric film-forming composition.
  • a coagulant layer is left on the former after the coagulant dipping step.
  • the coagulant layer on the former attracts a layer of film-forming composition onto the surface of the former, at a desired thickness that is dependent on the coagulant composition and concentration.
  • the polyol material into the elastomeric film by including the polyol material in the coagulant used in the production of the elastomeric film.
  • the distribution of polyol will be consistent with the polyol material being present in a coagulant composition used in the preparation of the elastomeric article.
  • the concentration of polyol may be greater at the former-contacting surface, which may become the outwardly- facing surface of the article after the elastomeric film is stripped from the former (i.e.
  • the articles are suitably disposable elastomeric articles - being of light weight and low cost, suitable for disposable after a period of use.
  • the articles may be thin film articles.
  • the articles may be dipped articles (i.e. articles produced from a dipped elastomeric film, composition may be applied by dipping or otherwise).
  • the elastomeric article is in the form of a glove or finger cot.
  • the elastomeric article is a clean-room glove or clean-room finger cot.
  • the dipped article when the dipped article is intended for clean room use, may have a total ionic content of less than or equal to 5 ⁇ g/cm 2 measured according to IEST-RP-CC005.4.
  • the total ionic content of the article may be not more than 4 ⁇ g/cm 2 , 4 ⁇ g/cm 2 , 3 ⁇ g/cm 2 , 3 ⁇ g/cm 2 , 2 ⁇ g/cm 2 , 2 ⁇ g/cm 2 , 1 ⁇ g/cm 2 , ⁇ g/cm 2 , O ⁇ g/cm 2 , O ⁇ g/cm 2 , O ⁇ g/cm 2 , O ⁇ g/cm 2 , or O ⁇ g/cm 2 .
  • the dipped article may have a total ionic content of less than or equal to 2 ⁇ g/cm 2 or 0.56 ⁇ g/cm 2 measured according to IEST-RP-CC005.4.
  • the polyol containing coated dipped elastomeric articles typically satisfy these ionic content requirements as they do not rely on an anti-static ionic material to provide their ESD properties.
  • the dipped article when the dipped article is intended for clean room use, the dipped article may have a liquid particle count of less than or equal to 5000 counts/cm 2 measured according to IEST-RP-CC005.4.
  • the liquid particle count may be less than or equal to 4500 counts/cm 2 , 4000 counts/cm 2 , 3500 counts/cm 2 , 3000 counts/cm 2 , 2500 counts/cm 2 , 2000 counts/cm 2 , 1500 counts/cm 2 , 1000 counts/cm 2 , 900 counts/cm 2 , 800 counts/cm 2 , or 350 counts/cm 2 .
  • the dipped elastomeric articles may have a liquid particle count of about 300-5000 counts/cm 2 after coating, for example, about 300-4000, about 300-3000, 300-2000 or 300-1000 counts/cm 2 after coating.
  • the coating layer does not substantially contribute to the total ionic content and/or liquid particle count measured according to IEST-RP-CC005.4.
  • the liquid particle count of a coated article may be within about 5% of the liquid particle count of the article prior to coating.
  • Articles containing lithium salts, alkali carboxylates and quarternary ammonium salts do not typically meet these ionic content limits, and liquid particle counts, since these ionic salts contribute to the total ionic content of the articles.
  • the dipped elastomeric articles contain releasable particle and/or extractable matter contents measured according to IEST-RP-CC005.4 suitable for clean room applications.
  • the thickness of the elastomeric film can, for example, be in the range 0.01 -3.0mm, such as 0.01 -1 .0mm, 0.01 -0.3mm, 0.02-0.2mm, 0.02- 1 .0mm, 0.05-0.10mm, 0.05-1 .0mm, 0.03-0.08mm, 0.03-1 .0mm, 0.05-1 .0mm or 0.05-0.08mm (for thin or disposable gloves and articles), and 0.2 - 3.0mm for thick gloves and articles.
  • the thickness is suitably measured as an "average thickness" for the article. In the case of gloves, the thickness is measured using an average of the thickness measurements taken at the three points described below.
  • the film thickness of a glove is less than 2mm (e.g. from 0.01 mm to 2mm).
  • the film thickness may be in the range of from 0.04mm to 2mm or 0.04mm to 1 .0mm.
  • the standard practice in the industry is to measure the thickness of the glove at three points - the cuff, the palm and the finger.
  • the finger thickness is measured 13 mm +/- 3mm from the fingertip; the palm thickness is measured at the centre of the palm, and the cuff thickness is measured at 25mm +/- 5mm from the cuff edge.
  • the average of the three measurements is taken to establish a glove thickness.
  • Thickness measurements are taken in accordance with the procedure specified in ASTM D3767-03 (Reapproved 2014).
  • the same technique is used to measure the thickness of other elastomeric film products, such as finger cots. In the case of finger cots, the film thickness is measured by reference to the finger thickness only.
  • the film thickness for a finger cot may be between any of the ranges indicated in the preceding paragraph, or from 0.01 mm to 2mm.
  • the glove may have a weight of between 0.5 and 20 grams.
  • the glove weight is a minimum of 0.5 grams, 1 .0g, 1 .5 g, 2.0g, 2.5g, 3.0g, 3.5g, 4.0, 4.5g, 5.0g, 5.5g, 6.0g, 6.5g, 7.0g .
  • the maximum weight may be about 20.
  • the glove weight will vary depending on the glove size (for example small, medium, large, etc.) and the length of the gloves (gloves may be made of varying lengths, for example, 9 inches or 12 inches in length). As one example, for gloves of 12 inch length the glove weight in some embodiments is less than about 8g, less than about 5g, from about 3.0g to about 9.0g, about 4.0g to about 8.0g, about 4.5g, about 6.0g or about 7.0g. In another example, for gloves of 9 inch length the glove weight in some embodiments is less than about 5g, from about 3.0g to about 5.0g, about 4.0g or about 4.5g. The glove weight in some embodiments is from about 3.0g +/- 0.4g.
  • the articles may comprise a single layer film, or a multilayered film and, where present, a coating layer.
  • the final film (article) may comprise from 1 to 15 layers.
  • there is a single elastomeric film layer in other embodiments there are 1 , 2 or 3 elastomeric film layers. In some embodiments, there are 2 or 3 elastomeric film layers.
  • Other coatings such as slip coatings or powder coatings to aid donning may also be present, but in some embodiments, the articles consist of the elastomeric film and the coating layer as described herein.
  • the elastomeric articles as described herein may retain those desirable elastomeric properties of the underlying elastomeric films, in spite of the inclusion of the polyol material.
  • the presence of a polyol material in the elastomeric article may result in some desirable changes to some properties of the film.
  • the presence of the polyol in the elastomeric article provides excellent softness and low modulus. These properties may act to minimise hand fatigue, thus improving productivity of the wearers with less muscle effort at work.
  • the elastomeric article has a tensile strength of 8MPa and above (e.g. from 8 MPa to 50 Mpa, from 14 Mpa and above, from 14 MPa to 25 MPa or from 8 MPa to 15 Mpa), a modulus at 300% of between 1 and 10MPa, (e.g. between 1 and 5 MPa, or between 1 MPa to 4 Mpa), a stress at 500% of up to 15 MPa (such as up to 10 MPa, between 1 and 5 MPa or 1 MPa to 4 Mpa), and/or an elongation to break of between 500% and 1000% (such as from 600% to 1000% or 700% to 1000%).
  • 8MPa and above e.g. from 8 MPa to 50 Mpa, from 14 Mpa and above, from 14 MPa to 25 MPa or from 8 MPa to 15 Mpa
  • a modulus at 300% of between 1 and 10MPa e.g. between 1 and 5 MPa, or between 1 MPa to 4
  • the elastomeric article has a tensile strength between 8 and 14 MPa, an elongation of between 600% and 1000% and/or a modulus at 300% of between 1 and 2.4 MPa.
  • a tensile strength between 8 and 14 MPa, an elongation of between 600% and 1000% and/or a modulus at 300% of between 1 and 2.4 MPa.
  • the tensile strength not less than 50%, not less than 60%, not less than 70%, not less than 80% or not less than 90% of that of the same article without said polyol material.
  • the polyol material may result in an increase in the elongation at break.
  • the elastomeric article has an elongation that is at least 10% greater than that of the same article without said polyol material, and preferably not more than 15%, 20%, 25% or 30% greater than that of the same article without said polyol material.
  • the elastomeric article has a modulus at 300% that is less than 80% of that of the same article without said polyol material, and preferably not less than 40%, not less than 50% or not less than 60% of that of the same article without said polyol material.
  • two or more of these requirements are combined. It is noted that the modulus at 300% values are based on unaged films.
  • the calculations of weight, thickness, modulus and elongation may be based on a sample of at least 10 articles (e.g. gloves or finger cots).
  • the elastomeric film-forming composition from which the elastomeric film is made comprises the elastomer and one or more cross-linking agents in a liquid medium.
  • the elastomeric film- forming composition may optionally comprise one or more polyol materials.
  • the liquid medium is typically water, although other solvents such as alcohols (including aliphatic alcohols and aromatic alcohols) or aromatic solvents may be used.
  • alcohols including aliphatic alcohols and aromatic alcohols
  • aromatic solvents may be used.
  • the total solids content of the elastomer component of the elastomeric film-forming composition is from 5% to 60% by weight of the composition.
  • the percentage of total solids content (TSC%) can vary within this range.
  • the total solids content of the elastomer component of the elastomeric film-forming composition is about 5 to 55%, 10 to 60%, 10 to 55%, 15% to 60%, 15% to 55%, 20% to 60%, 20% to 55%, 5% to 50%, 10% to 50%, 20% to 50%, 30% to 60%, 30% to 55%, 30% to 50%, 35% to 60%, 35% to 50%, 40% to 60%, 40% to 55%, 40% to 50%, 45% to 60%, 45% to 55% or 45% to 50%.
  • the elastomeric film may be a self-supported or unsupported film.
  • a self-supported or unsupported film is a film that exists without other structural components or layers that the film is adhered to or attached to.
  • Elastomer-forming polymers include natural rubber and synthetic elastomer-forming polymers, which can be cross-linked to produce elastomeric films.
  • the polymer may be a single polymer or a combination of two or more polymers.
  • the polymer may be a homopolymer or a copolymer, or a blend of polymers/co polymers.
  • the synthetic elastomer-forming polymer may be a polymer containing free ionically cross- linkable groups, covalently cross-linkable groups, or a combination of both.
  • ionically cross-linkable groups are acids, including carboxylates, sulfonates and acid anhydrides, and an example of a covalently cross-linkable group is a double bond.
  • the elastomer-forming polymers may be selected from rubber (natural or synthetic), nitrile rubber, polyurethane, polyisoprene, polychloroprene, acrylic polymers (including acrylic diene block copolymers), polybutadienes, copolymers of these and other
  • polymers/monomers random copolymers, block copolymers or otherwise
  • modified forms of these polymers or copolymers e.g. polymers containing additional substituents such as carboxylate, sulfonate, halide or other substituents.
  • the only elastomers in the elastomeric film are those selected from the group consisting of natural rubber, nitrile rubber, polyurethane, polyisoprene, polychloroprene, polystyrene, acrylic polymers, polybutadienes, and copolymers or blends of these polymers or their monomers.
  • Synthetic elastomer-forming polymers include copolymers produced by copolymerisation of conjugated diene monomers and ethylenically unsaturated acid monomers (carboxylated polyacrylonitrile butadiene being an example of such a copolymer), polyisoprene, polychloroprene, styrene copolymers and/or polyurethane.
  • examples are 1 ,3-butadiene, iso-prene, 2,3-dimethyl-1 ,3-butadiene, 2- ethyl-1 ,3-butadiene, 1 ,3-pentadiene, chloroprene and acrylonitrile.
  • the acid group may be a carboxyl group, a sulfonic acid group or an acid anhydride group.
  • ethylenically unsaturated acid monomers include acrylic acid or methacrylic acid; itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, sytrenesulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2- hydroxypropyl maleate, and alkali metal or ammonium salts thereof.
  • the polymers used may be carboxylated or non-carboxylated, as desired.
  • polyacrylonitrile butadiene This may be carboxylated or non-carboxylated. This may be provided as a mixture of carboxylated nitrile latex and nitrile butadiene rubber.
  • Carboxylated refers to the presence of carboxylate (carboxylic acid or ester) groups on the polymer chain. Carboxylation may be achieved by forming the polymer with a monomer containing carboxylate groups, or through grafting carboxylate groups to a polymer.
  • suitable carboxylated polymers reference is made to PCT/AU2014/000726 and PCT/AU2014/000727, the entirety of each being incorporated into this specification by reference.
  • the degree of carboxylation may be between 5-15% (or 5-10%).
  • the amount of the elastomer is 100 phr (per hundred parts "rubber"), and for the relative amounts of the remaining components of the elastomeric composition to be calculated as a number of parts compared to the 10Ophr of the elastomer, by weight.
  • the amount of cross-linking agent is referred to as 1 .0 phr.
  • Elastomer-forming polymers can be cross-linked with one or more cross-linking agents to produce the elastomeric film.
  • cross-linking agents can be used.
  • Other agents that may be present in the composition used to produce the elastomeric film-forming composition include one or more polyol materials as described above, plasticizers, anti- ozonants, stabilisers such as pH stabilisers, surfactants, emulsifiers, antioxidants, vulcanising agents, accelerators, polymerisation initiators, pigments, fillers, colourising agents and sensitisers. Many of these agents are added in particulate form. Others are added as liquids. These are added prior to forming the latex composition into the shape of the synthetic elastomeric article.
  • agents including plasticizers, anti-ozonants, stabilisers such as pH stabilisers, surfactants, emulsifiers, antioxidants, vulcanising agents, accelerators, polymerisation initiators, pigments, fillers, colourising agents, rubber reoderants, wetting agents, defoamers and sensitisers may be present in the composition used to produce the elastomeric film-forming composition as described in PCT/AU2014/000726, PCT/AU2014/000727, PCT/AU2016/050308,
  • Cross-linking agent classes include ionic cross-linking agents and covalent cross-linking agents.
  • the cross-linking agent or agents used in the production of the elastomeric film may be selected from ionic cross-linking agents, covalent cross-linking agents, and combinations thereof. The selection will depend on various factors including the properties of the film desired and the choice of elastomer.
  • Ionic cross-linking agents include metal oxide cross linking agents (such as zinc oxide and magnesium oxide), peroxides (such as 1 ,1 -di(t-butylperoxy)-3,3,5-trimethylcyclohexane, which can be purchased under the trade name Trigonox 29-40B-pd) and solubilized ionic cross-linking agents such as negatively charged multivalent metal complex ions including solubilised sodium aluminate.
  • metal oxide cross linking agents such as zinc oxide and magnesium oxide
  • peroxides such as 1 ,1 -di(t-butylperoxy)-3,3,5-trimethylcyclohexane, which can be purchased under the trade name Trigonox 29-40B-pd
  • solubilized ionic cross-linking agents such as negatively charged multivalent metal complex ions including solubilised sodium aluminate.
  • Other ionic cross-linking agents amongst those known in the art can be used. These include the cross-linking agents described in PCT
  • Covalent cross-linking agents include organic cross-linking agents, sulphur and/or sulphur donors, and combinations thereof.
  • Sulphur may be added in the form of elemental sulphur.
  • Sulphur donors are another way of providing sulphur cross-linking. Sulphur donors release sulphur, or act with sulphur- containing compounds, to accelerate sulphur-based covalent cross-linking of the elastomer- forming polymer.
  • sulphur donors can be advantageous as they shorten the curing (vulcanisation) time, lower the curing temperature or decrease the amount of cross-linking agents required to be used in the composition.
  • sulphur donors can give rise to allergic reactions, such as allergic contact dermatitis with symptoms including erythema, vesicles, papules, pruritus, blisters and/or crusting.
  • sulphur donors may also be referred to as accelerators.
  • suitable sulphur donors include the carbamates such as thiocarbamates (e.g. zinc dibutyl dithiocarbamate (ZDBC), Zinc diethyl dithiocarbamate (ZDEC); Zinc dimethyl dithiocarbamate (ZDMC); thiurams (e.g. tetraethylthiuram disulfide (TETD), Tetramethylthiuram disulphide (TMTD));
  • thiocarbamates e.g. zinc dibutyl dithiocarbamate (ZDBC), Zinc diethyl dithiocarbamate (ZDEC); Zinc dimethyl dithiocarbamate (ZDMC); thiurams (e.g. tetraethylthiuram disulfide (TETD), Tetramethylthiuram disulphide (TMTD));
  • DPTT Dipentamethylene thiuram tetrasulfide
  • DPTH Dipentamethylene thiuram hexasulfide
  • thiourea Ethyl thiourea (ETU) and diphenylthiourea (DPTU)
  • thiazoles e.g. Mercapto Benzothiazoles (MBT), Mercapto Benzothiozole disulphide (MBTS), zinc 2-mercaptobenzothiazole (ZMBT)
  • guanidines e.g. Diphenylguanidine (DPG)
  • aldehyde/amine-based sulphur donors e.g.
  • any amount of cross-linker may be used, as required for the final article properties.
  • the total amount of cross-linking agents in the composition may be between 0.01 and 14 phr.
  • the total cross-linking agent amount may be within one of the following ranges: 0.01 - 14.5phr, 0.2 - 12.5phr, 0.3 - 10 phr, 0.1 - 10 phr, 0.2 - 10 phr, 0.3 - 9 phr, 0.5 - 9 phr, 0.8 - 9 phr, 0.3 - 8 phr, 0.5 - 8 phr, 0.8 - 6 phr, 1 - 5 phr, 2 - 9 phr, 3 - 10 phr, 3 - 7 phr, 1 - 3 phr, 0.01 - 0.5 phr, 0.01 - 1.0 phr.
  • the amount of ionic cross-linking agent may be between 0.0 - 4.0 phr, such as 0.01 - 4.0.
  • the amount is preferably lower still, at 0.01 - 3.0 phr, or 0.01 - 2.0 phr, 0.01 - 1 .0 phr or 0.01 - 0.5 phr.
  • the amount of sulphur may be between 0.0 - 5.5 phr.
  • the amount may be lower still, at 0.0 - 3.5phr, such as 0.01 - 3.0phr, 0.01 - 2.0phr, 0.01 - 1 .5phr, 0.01 - 1 .Ophr or 0.01 - 0.5phr.
  • the amount of sulphur donor may be between 0.0 - 2.0 phr, such as between 0.1 - 1 .5phr, 0.1 - 1 .Ophr, 0.2-1 .Ophr, 0.3 - 2. Ophr, 0.3 - 1 .5phr or 0.2-0.6phr.
  • the amount of organic cross-linking agent may be between 0.0 - 4.0 phr, such as 0.01 - 4.0.
  • the amount may be lower still, at 0.01 - 3.0 phr, or 0.01 - 2.0 phr, or 0.01 - 1 .0 phr.
  • the cross-linking agent can be combined with the latex composition and other components of the elastomeric film-forming composition at suitable time points for the formation of the desired type of film.
  • Cross-linking agents are typically added to the latex composition with other components, however for some forms of cross-linking agent (such as the solubilised ionic cross-linking agents, including sodium aluminate) there is a preliminary step involving the formation of a cross-linking composition and combining this with the latex under controlled conditions, followed by the addition of other components and secondary cross- linking agents.
  • the elastomeric film-forming composition from which the film is made contains one or more polyol materials. It is noted that this component is optional in the elastomeric film-forming composition, since there is polyol present in the coating layer that provides ESD properties.
  • the polyol material in the elastomeric film-forming composition may be a polyol selected from the polyethylene glycols (PEG), such as PEG 300.
  • PEG polyethylene glycols
  • the polyol material may be present in a concentration of from about 0.01 phr to 60 phr, or preferably less than 30 phr. Where a mixture of two or more polyol materials is added to the elastomeric composition, the total concentration of polyol materials (i.e. the concentration of the mixture of polyol materials) is from about 0.01 phr to 60 phr, or preferably less than 30 phr.
  • the amount of polyol material added to the latex composition will depend on the type of elastomer and cross-linking agent that is used. In some embodiments, the polyol material is in the elastomeric film-forming composition is from 0.01 to 60 phr, preferably less than 30 phr.
  • the amount of polyol material present in the elastomeric article is 0.01 to 60 phr, 0.01 to 55 phr, 0.01 to 50 phr, 0.01 to 45 phr, 0.01 to 40 phr, 0.01 to 30 phr, 0.01 to 28 phr, 0.01 to 26 phr, 0.01 to 23 phr, 0.01 to 20 phr, 0.01 to 18 phr, 0.01 to 15 phr, 0.01 to 12 phr, 0.01 to 10 phr, 0.05 to 60 phr, 0.05 to 50 phr, 0.05 to 40 phr, 0.05 to 30 phr, 0.05 to 28 phr, 0.05 to 26 phr, 0.05 to 23 phr, 0.05 to 20 phr, 0.05 to 18 phr, 0.05 to 15 phr, 0.05 to 12 phr, 0.05 to 10 phr, 0.01 to
  • the total amount of polyol material present in the final elastomeric article i.e. the amount of the mixture of polyol materials
  • the total amount of polyol material present in the final elastomeric article is within the amounts indicated above for a single polyol material.
  • the elastomeric film-forming composition may additionally contain a conductive polymer.
  • Conductive polymers include polypyrrole-based and polyaniline-based conductive polymers.
  • conductive polymers reference is made to US 6,235,660, incorporated herein in its entirety by reference.
  • the elastomeric composition used to form an elastomeric article comprises:
  • a dispersion of a film-forming elastomer such as nitrile, natural rubber, chloroprene, isoprene, polyurethane or mixtures thereof;
  • a pH adjustor such as potassium hydroxide, ammonia, sodium hydroxide or a mixture thereof;
  • crosslinking agents such as sulphur, sulphur donor, metal oxide, ionic crosslinking agent and the like;
  • An accelerator such as dithiocarbamate, thiuram, mercapto and the like.
  • one or more additional components selected from anti-oxidant, anti-ozonant, wetting agent, emulsifier, defoamer, stabilizer, rubber deodorant, colour pigment, opacifier and the like.
  • the elastomeric film-forming composition having the desired components is formed into the shape of the desired article, and then cured. Curing is used in a general sense, to refer to the stage during which cross-linking is performed. Such curing conditions are as known in the art.
  • the elastomeric film is suitably prepared by a dipping process.
  • Optional step (a) Dipping the former into a coagulant containing multivalent ions in solution
  • a suitable former which is based on the shape of the article to be produced (e.g. glove- shaped for a glove or finger-shaped for a finger cot) can be dipped into a coagulant (i.e. a coagulant composition) containing multivalent ions in solution.
  • the former is dipped into a coagulant containing multivalent ions, leaving a thin coating of the charged ions on the surface of the former.
  • the charged ions coating can assist in controlling the amount of the composition for forming the elastomeric film that will subsequently remain on the surface of the former after dipping into the composition, through charge interactions.
  • the ions may be cationic (as in the case of, for example, sodium ion-containing coagulants or calcium ion-containing coagulants) or anionic, and the choice will be based on the identity of the elastomeric polymer.
  • the coagulant will have a pH greater than 7, such as pH 8 to 10.
  • metal ion solutions containing cations are suited to a broad range of elastomeric polymers.
  • metal salt ions are sodium, calcium, magnesium, barium, zinc, and aluminium.
  • the counter ions may be halides (such as chloride), nitrate, acetate or sulphate, amongst others.
  • the calcium ions can be provided as a solution of calcium nitrate or calcium chloride.
  • the concentration of ions in the coagulant can broadly be in the range of 0.0 - 50% by weight of the coagulant composition (measured as the compound of the multivalent ion in the solution of the multivalent ions), depending on the desired thickness of the elastomeric film layers and the number of layers to be applied (i.e. one layer or two or more layers).
  • the concentration is suitably in the range of 0.0 - 20%, 0.0 - 15%, 0.0 - 12%, 1 .5 - 20%, 1 .5 - 15%, 1 .0 - 10%, 1 .5 - 10%, 4 -10%, 5 - 10%, 5 - 35%, 10 - 30%, 7 - 40%, 8 - 50% and 5 - 45%.
  • the concentration is in the range of 10 - 30%.
  • the amounts of other components such as wetness and anti-tack agents are dependent on the properties desired through the use of these agents, and will vary accordingly.
  • the coagulant composition may also contain a polyol material or a mixture of polyol materials as described above.
  • the polyol material may be added to the prepared coagulant or the polyol material may be combined with the other basic components of the coagulant composition during the formulation of the coagulant composition.
  • the polyol material present in the coagulant composition may have a melting point and/or a cloud point of above 50°C.
  • the polyol material present in the coagulant composition may be selected from glycerine, PEG 6000, PEG 300, PEG 7 glyceryl cocoate, polysorbate 80 and sorbitol.
  • the polyol material may be present in the coagulant composition in a concentration in the range of at least about 0.001 %, or preferably 0.1 % to 30% by weight of the coagulant composition.
  • the amount may be within the range of: 0.1 % to 25%, 0.1 % to 22%, 0.1 % to 20%, 0.2% to 30%, 0.2% to 25%, 0.2% to 22%, 0.2% to 20%, 0.5% to 30%, 0.5% to 25%, 0.5% to 22%, 0.5% to 20%, 0.5% to 18%, 0.8% to 27%, 0.8% to 23%, 0.8% to 18%, 1 % to 15%, 1 % to 20%, 5% to 22%, 5% to 18%, or 5% to 12% by weight of the coagulant composition.
  • the total concentration of polyol materials may be within any of the ranges set out immediately above.
  • the coagulant may also include any other agents, such as wetting agents (such as fatty alcohol ethoxide or other suitable surfactants), anti-tack agents, anti-foaming agents and/or mould release agents, such as silicon emulsions, polymer release agents and metallic stearates, examples of which are zinc, calcium and potassium stearates.
  • the coagulant may also include metallic stearates in a concentration in the range of about 0.1 -5.0% by weight, suitable wetting agents in a concentration in the range of about 0.001 - 1 .0%, and/or antifoaming agents in a concentration in the range of 0.001 -1 .0% by weight.
  • the time period over which the former is lowered into the coagulant may be between 1 and 30 seconds, such as 2-30 seconds, 1 -10 seconds, or 1 -5 seconds. Then, the duration or dwell time for the mould in the coagulant is suitably between 0.1 and 50 seconds, such as between 1 and 50 seconds or between 1 and 30 seconds. In some embodiments, the dwell time for the former in the coagulant is 1 to 10 seconds. In some embodiments, the dwell time for the former in the coagulant may be longer than 30 seconds. The time period over which the former is removed from the coagulant may be between 1 and 30 seconds, such as between 3 and 30 seconds or between 1 and 10 seconds. The total time period may, in one embodiment, be between 10-24 seconds.
  • the temperature of the coagulant into which the former is dipped may, for example, be between 30°C - 80°C, 30°C - 49°C, 35°C - 45°C, or 35°C - 50°C. It is noted that the preferred temperature ranges for the coagulant dipping step are below the melting point and/or cloud point indicated above for the polyol material, which is above 50°C.
  • the time period for lowering covers the time from when the former first touches the liquid composition until complete immersion (i.e. the lowest point of immersion).
  • the time period of removal or raising covers the time from the commencement of raising of the former until the point at which the former is completely removed from the liquid composition, and just breaks contact with the liquid surface.
  • time periods indicated herein for dipping times are dependent on the speed of the production of line for glove production, and the size of the tanks present in the production line. These dipping time periods suit about 3.3 to 8 metres of effective length of coagulant and a linear speed of 20 metres/minute.
  • the latex dipping times indicated blow suit 5-8 metres of effective length of latex at the same linear speed. Adjustments can be made for production lines with different tank lengths, and different linear speeds.
  • the former is dipped into a coagulant, following this step the former is dried or partially dried.
  • Step (i) Dipping the former into the elastomeric film-forming composition of the invention to produce a layer of elastomeric film-forming composition on the mould
  • the former is dipped into the composition for producing an elastomeric film, embodiments of which have been described in detail above.
  • the duration of dipping, temperature, and former surface temperature may be as described in the PCT publications referred to above.
  • the duration of dipping, or the dwell time refers to the time taken from the point at which the glove former is completely immersed into the composition, until the point at which the glove former commences being removed from the composition.
  • the former is in the dipping tank for an amount of time to ensure the former is evenly coated, but not so long as to develop a thicker coating than necessary.
  • the time period over which the mould is lowered into the dipping tank or latex composition may be between 1 and 30 seconds, such as 2-30 seconds or 1 -10 seconds.
  • the dwell time of the former in the dipping tank may be between about 1-60 seconds, such as between about 5 to 60 seconds, 1 to 30 seconds, 1 to 10 seconds or 2.0 to 7.0 seconds.
  • the time period over which the mould is removed from the latex may be between 1 and 30 seconds, such as 3-30 seconds, 1 -30 seconds or 1 -20 seconds. In some embodiments, the total time period may be between about 3 to 50 seconds, such as 5 to 30 seconds.
  • the temperature of the composition into which the former is dipped is generally within the range of 10°C to 60°C, such as 10°C to 50°C, 15°C to 50°C, 20°C to 50°C, 25°C to 50°C, 25°C to 45°C, 20°C to 40°C or 20°C to 35°C.
  • the composition into which the former is dipped is constantly cooled with chilled water and the latex bath temperature is kept between 20 - 35° C, such as 20° C to 30°C and more preferably at 25°C.
  • the composition is constantly circulated in the tank to avoid creaming and settling of the chemicals contained in the elastomeric film-forming composition.
  • step (v) If a single film-layer glove is produced, the next step performed is step (v).
  • Step (ii) Drying or partially drying the layer of elastomeric film-forming composition on the former
  • the method of manufacture described herein encompasses the preparation of single- layered or multiple-layered elastomeric films. Therefore, in some embodiments, the method may include step (v), which involves drying and curing the layered elastomeric film on the former directly after this step to prepare a single layered elastomeric film. In other embodiments, the method may include a number of repetitions of optional steps (iii) and (iv) after this step to produce a multiple-layered elastomeric film.
  • Step (iii) Optionally dipping the former coated with the dried or partially dried layer of elastomeric film-forming composition into the elastomeric film-forming composition to produce a further layer of elastomeric film-forming composition on the former
  • This step is optional, and is present when multi-layer articles are produced.
  • the details of this step are as described in the PCT publications referred to above.
  • the conditions for the second dip may be the same as those for the first dip, or this dip may be performed at a different total solid content, and for a shorter dwell time.
  • the second elastomeric film- forming composition into which the former is dipped may be the same as that for the first dip, or it may be different.
  • the first composition may contain a polyol material, and the second composition may be free of polyol material, or vice versa.
  • Step (iv) Optionally repeating the drying or partial drying step (ii) and the further dipping step (Hi)
  • This step is optional, and is present when multi-layered articles are produced.
  • the number of layers may be 2, 3 or more in multi-layered articles.
  • the details of this step are as described in the PCT publications referred to above.
  • Step (v) Optional additional steps prior to drying and curing
  • the film or article can be leached to remove extractable components, there may be a coating material applied, beading/cuffing cab be performed and/or the product may be passed through a curing or vulcanizing oven to evaporate the water in the film and enable better cross linking.
  • Step (vi) Drying and/or curing the layered elastomeric film on the former
  • This step is optional. The details of this step are as described in the PCT publications referred to above.
  • additional optional steps that can be performed prior to stripping of the glove from the former include cooling, chlorination, post-curing rinsing, polymer coating and additional drying steps.
  • the cured film may also be cooled / chlorinated / neutralized and/or - post-leached in hot water.
  • One additional step that may be performed, as described below, is coating with a coating composition comprising a polyol material. However, the coating step may be one that is performed following stripping.
  • Step (ix) Optionally applying a coating composition comprising a polyol material to form a coating layer on the elastomeric article
  • An elastomeric article that is formed by the technique described above may be coated with a coating composition comprising a polyol material to produce an elastomeric article having electrostatic dissipative (ESD) properties.
  • a pre-formed elastomeric article that is prepared by any method may also be coated with a polyol material or a coating composition containing a polyol material to produce an elastomeric article having electrostatic dissipative (ESD) properties.
  • ESD electrostatic dissipative
  • the elastomeric articles produced from method set out in steps (i) to (viii) above may already contain a polyol material.
  • the elastomeric article may be produced with a polyol material present in the elastomeric composition and/or the coagulant, as well as having a polyol material-containing coating.
  • dried or partially dried elastomeric articles are stripped from the formers (step (viii) above) and placed in the tumble dryer.
  • a coating composition is prepared which comprises the polyol material.
  • the coating composition typically comprises a solvent to aid in application of the desired amount of the polyol material to the articles.
  • the coating composition may be applied in the tumble dryer via a pump sprayer or through addition of the liquid coating composition into the dryer by another technique. In the case of spraying, spraying occurs while the articles are tumbled to ensure that the coating composition is applied evenly on each glove.
  • the volume of coating composition applied may typically be in the range of about 0.01 L or more.
  • Drying in the tumble dryer results in evaporation of the solvent component of the coating composition, to leave the polyol material (and any other non-volatile components) on the surface of the elastomeric article. Drying typically continues in the tumble dryer for a further time period of at least 5 minutes (preferably 60 to 120 minutes), at a temperature of more than 35°C (preferably 50 to 70°C), after all of the coating composition has been applied. Finally, the coated articles are discharged from tumble dryer before being submitted for quality control and packing processes.
  • the coating composition may alternatively be applied through soaking of the elastomeric articles in the coating composition.
  • the dried or partially dried articles stripped from the formers are transferred into a vessel.
  • the coating composition is added to the vessel and the articles are soaked in the coating composition for at least 30 seconds (preferably 10 to 30 minutes).
  • the articles are then transferred into a tumble dryer for drying at a temperature of more than 30°C (preferably 50 to 70°C) for more than 10 minutes (preferably 60 to 120 minutes).
  • the coating composition may alternatively be applied through application of the coating composition in a washer.
  • the articles are then transferred into a tumble dryer for drying at a temperature of more than 30°C (preferably 50 to 70°C) for more than 10 minutes (preferably 60 to 120 minutes).
  • the coating composition is applied to the elastomeric article online during the article manufacturing process.
  • This technique involves dipping of the elastomeric film on the former into a coating composition comprising the polyol material.
  • the coating is on the surface of the cured elastomeric film that will be the outwardly-facing ("outer" or "external") surface of the article.
  • the cured elastomeric film on the former is dipped into the coating composition comprising the polyol material.
  • the coating composition may then be dried while the elastomeric article is on the former, and then the article is stripped form the former.
  • the coating composition may be acrylate-free, hydrogel-free, silicon-free, phthalate-free, lithium salt-free and/or quaternary ammonium salt-free. In some embodiments, the coating composition is free of all of these agents.
  • the coating composition may contain the polyol material in a concentration of at least about 0.0005 or at least about 0.001 % by weight of the coating composition.
  • the coating composition contains the polyol material in a concentration of or preferably 0.01 % to 40%, 0.01 % to 35%, 0.01 % to 22%, 0.01 % to 20%, 0.1 % to 40%, 0.1 % to 35%, 0.1 % to 30%, 0.1 % to 25%, 0.1 % to 22%, 0.1 % to 20%, 0.2% to 30%, 0.2% to 25%, 0.2% to 22%, 0.2% to 20%, 0.5% to 30%, 0.5% to 25%, 0.5% to 22%, 0.5% to 20%, 0.5% to 18%, 0.8% to 27%, 0.8% to 23%, 0.8% to 18%, 1 % to 15%, 1 % to 20%, 5% to 22%, 5% to 18%, 5% to 12% by weight of the coating composition.
  • the coating composition comprises two or more different polyol materials
  • the total concentration of polyol materials is within any of the ranges indicated above.
  • the articles or gloves are further processed as described below. It is noted that this procedure is performed prior to application of any coating layer, if the incorporation of polyol material is through the coating technique.
  • the dried or partially dried elastomeric articles are optionally placed in the tumble dryer and tumbled at a temperature of about 30°C to about 140°C for about 5 to about 240 minutes. In this step, the articles may loosen and further curing of the articles may occur.
  • the articles are then placed into a washer. Chlorinated water containing 50 to 1500 ppm of chlorine is added into the washer, and the articles are treated for about 30 seconds to about 30 minutes. An anti-chlorine solution is added into the washer to rinse and to neutralize the chlorine residue, and the articles are treated with this solution for about 30 seconds to about 30 minutes.
  • a surfactant such as an anionic surfactant, a cationic surfactant, a non-ionic surfactant or an amphoteric surfactant
  • the surfactant is a non-ionic surfactant, such as an alcohol ethoxylate non-ionic surfactant.
  • the washer is then filled with deionized or multi-filtered water.
  • the articles are then washed for about 1 minute or more (preferably about 10 to about 30 minutes) for each wash.
  • the washing step may be repeated to achieve a desired liquid particle count and ionic content.
  • the washing step may be repeated 1 or more times, preferably the washing step is repeated 2 to 20 times, 3 to 15 times, 4 to 10 times or 3 to 8 times.
  • additional washing steps may be conducted with at least 1 round, and preferably 2 to 5 rounds, of either washing in hot deionized water or hot multi-filtered water. In some cases a temperature of 40 to 80°C is required.
  • Spinning is then used to remove water from the articles before they are transferred to a tumble dryer located in a clean room environment.
  • the gloves are dried in the dryer at about 35°C or more, preferably about 50°C to 70°C for about 20 minutes to about 240 minutes, or until the articles are completely dried.
  • the elastomeric articles produced by this method may optionally be further processed, such as by the application of a coating composition comprising the polyol material to form a coating layer on the elastomeric article, as described in step (ix) above.
  • the present application also extends to finger cots and methods for their manufacture.
  • Finger cots are disposable shields for the finger only, and are used in situations when a full glove is not necessary. Finger cots can be made by the same technique as described above for glove production, with the one difference being the shape of the mould and the consequent shape/size of the product.
  • a finger cot comprises a finger portion and a beaded rim. In the case of finger cots, the finger thickness is the indicator of the thickness of the overall product.
  • the conditions for manufacture of the finger cot are as described above for the glove, with one exception.
  • the exception is that the time period of dipping the mould into the coagulant, and into the latex (covering lowering, dwell, and raising), is shorter due to the smaller size/length of the mould which requires less time to lower and raise to become fully immersed in the coagulant or latex.
  • the total time period is suitably half those specified for glove production indicated above.
  • a polyol material includes one, two or more polyol materials.
  • the polyol material is defined as having a particular identity, for example where the polyol material is said to be a polyethylene glycol with a molecular weight between 200 and 20,000, it will be understood that this is a reference to the single polyol material, or one of the polyol materials if more than one polyol material is present.
  • V Tribo-electrical charge
  • seconds Static decay time
  • Liquid particle count and ionic content Liquid particle count and ionic content.
  • Triboelectric charge is tested according to an in-house method modified from triboelectric charge generation method described in ESD TR 03-99, ESD Association Technical Report for the Protection of Electrostatic Discharge Susceptible Items - ESD Glove and Finger Cots. Briefly, cleaned vinyl glove is worn on both hand of technician. One hand of technician picking up the test glove at cuff, another hand holding a hand held non-contacting electrostatic voltmeter pointing the test glove surface. The hand held non-contacting electrostatic voltmeter moving from cuff to finger and finger to cuff for 3 cycles to measure electrostatic surface voltage on the glove surface. The electrostatic surface voltage is recorded as triboelectric charge before rub. Put down the hand held non-contacting electrostatic voltmeter while the other hand still holding the test glove.
  • Cuff area of the test glove is placed at crook in between thumb and forefinger of the technician's hand that was holding the voltmeter previously.
  • the test glove is held tightly by contacting the non-measurement surface with thumb and measurement surface with the other four fingers. Rubbing is conducted by moving the hand from cuff to finger area of the test glove for 5 times. Close contact of technician's hand and the test glove when rubbing is necessary to ensure electrostatic charge is generated on the test glove surface.
  • the hand held non-contacting electrostatic voltmeter is picked up again quickly to measure electrostatic charge on the test glove surface after rubbing by using the same measurement procedure described previously.
  • the electrostatic surface voltage is recorded as triboelectric charge after rub.
  • Static decay is tested according to procedure described in FTMS-101 Method 4046, Federal Test Method Standard - Test Procedures for Packaging Material - Electrostatic Properties of Materials.
  • Tensile strength, stress at 300% and 500% modulus and elongation to break are measured in accordance with ASTM D412, American Standard Test Method - Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers— Tension.
  • Example 1 Polyol Material Added into Glove Coating
  • the gloves were produced in accordance with the control composition set out in Table 1 below using standard elastomeric film production processes as known in the art.
  • the gloves produced had a glove length of 12 inches, an average thickness of 0.7 ⁇ 0.02 mm and a weight of 4.5g.
  • Gloves were coated using the compositions set out below using standard coating processes as known in the art.
  • Example 2 ESD properties of gloves coated with PEG300 at varying concentrations
  • Example 3 ESD properties of gloves coated with polyglycerol fatty acid ester at varying concentrations
  • Example 4 ESD properties of gloves coated with sorbitol at varying concentrations
  • Example 5 ESD properties of gloves coated with various polyols at various concentrations Table 8 - Polyol material containing coating composition
  • the examples shown herein indicate that the presence of a polyol material in a glove coating provides good electrostatic dissipative properties.
  • This example was conducted to explore whether the application of a coating composition comprising a polyol material would affect the physical properties of the gloves. For example, the question arises as to whether the application of a coating comprising polyol materials such as PEG and polyglycerol fatty acid ester has a positive or negative impact on the physical properties of the elastomeric composite. Tests were conducted to assess the impact of applying a coating composition comprising a polyol has on the glove, beyond the provision of an electro-dissipative effect. One possible outcome is that the polyol could soften the glove, which may in turn minimise hand fatigue of the wearer.
  • Seven gloves were prepared using the coating compositions defined above, with the control gloves containing no polyol material and having no polyol-containing coating, set 1 to 3 containing PEG 300 (in Table 16) and set 1 and 2 (in Table 17) containing polyglycerol fatty acid ester in the coating composition. These gloves were then tested for their physical properties.
  • polyol material applied in a coating layer on a surface of an elastomeric film may to some extent migrate into and be embedded within the film itself, resulting in the softening of the film observed in the test results.
  • this class of polyol material i.e. polyols or polyol esters
  • Example 7 ESD properties of gloves coated with polyglycerol fatty acid ester at various concentrations
  • Three gloves were prepared using the coating composition defined above, with the control containing no polyol and having no polyol-containing coating, and set 1 and 2 having 2 and 3% polyglycerol fatty acid ester present in the coating composition. These gloves were then tested for their surface resistivity (shown in Table 12) and tribo-electrical charge (V) (shown in Table 13).
  • Example 8 ESD properties of gloves coated with polyglycerol fatty acid ester and glycerine at various concentrations
  • the coating solution is prepared by dissolving the polyol material in deionized water. The mixture is stirred for 30 minutes. The coating solution is then sprayed on gloves that go through a washing process in the clean room process set out in the description above.
  • Example 9 ESD properties of gloves coated with a blend of PEG 300 and other polyol materials at various concentrations
  • the coating solution is prepared by dissolving the polyol material in deionized water. The mixture is stirred for 30 minutes. The coating solution is then sprayed on gloves that go through a washing process in the clean room process set out in the description above.
  • Example 10 Poly-glycerol fatty acid ester coating, manufacturing method and performance data (cleanliness, ESD properties & physical properties)
  • Gloves were prepared from the following composition set out below using standard elastomeric film production processes as known in the art.
  • Gloves for use in clean room environment need to be washed to remove excessive particles. Cleanliness of clean room environment is classified according to ISO 14644-1 or US FED STD 209E. In order to produce clean room gloves suitable for use in different cleanliness classification, the gloves must comply with the liquid particle count requirements. Washing process listed in table 21 below is used to produce clean room gloves that are suitable for use in cleanroom environments with different cleanliness classes.
  • the washed gloves were removed from washer and placed into tumble dryer for drying.
  • the gloves were dried for 120 minutes at temperature of 70 to 90 °C.
  • polyol coating solution prepared according to composition listed in table below was sprayed into the dryer.
  • the gloves were spun continuously inside the dryer to allow the polyol solution coated evenly on the surface of glove.
  • Each piece of 4.5g nitrile glove consists of 0.05g of dried polyol or 1 .1 1 % of polyol by weight of a 4.5g nitrile glove.
  • Control gloves were produced with the same washing and drying process, however, no polyol was coated on the gloves.
  • Cleanliness of the gloves was determined by measuring liquid particle count and ionic content extracted from the gloves. Liquid particle count and ionic content of the glove were tested in accordance with method stated in IEST-RP-CC005.4. Surface resistivity, triboelectric charge and static decay time of the gloves were tested in accordance with ASTM D257, modified method from ESD TR-03-99 and FTMS-101 Method 4046, respectively.
  • Table 23 below details the liquid particle count of polyol coated gloves and gloves without polyol coating.
  • Table 24 details the ionic content extracted from nitrile gloves with and without the polyol coating.
  • Cleanliness (liquid particle count and ionic content) of the polyol coated nitrile gloves was not affected by the polyol coating on glove surface. Liquid particle count and ionic content of the polyol coated gloves was comparable with control gloves without any polyol coating. Table 25 below is ESD properties of nitrile gloves with and without polyol coating.
  • the polyol coated nitrile gloves showed better ESD properties compared with control gloves without polyol coating.
  • Table 26 details physical properties of unaged nitrile glove with and without a polyol coating.
  • Nitrile clean room gloves coated with polyol showed higher elongation compared to control gloves without polyol coating.
  • Example 11 Combination of Polyol with non-polyol material
  • Table 28 above shows the surface resistivity of nitrile glove coated with polyol compositions Set 1 to 24 compared to control nitrile glove without polyol coating.
  • Example 12 Comparison of ionic anti-static coating with anti-static polyol coating on a nitrile glove
  • Table 29 below provides details of compositions of glycerine and potassium acetate in coating solutions used to coat dipped elastomeric articles in the form of gloves.
  • Sets 1 and 2 are based on ESD coatings described for the carpet compositions described in US3658744. In each set, the gloves were coated using standard coating processes.
  • Cleanliness of the gloves was determined by measuring liquid particle count and ionic content extracted from the gloves. Liquid particle count and ionic content of the glove were tested in accordance with method stated in IEST-RP-CC005.4. Surface resistivity, triboelectric charge and static decay time of the gloves were tested in accordance with ASTM D257, modified method from ESD TR-03-99 and FTMS-101 Method 4046.
  • Table 30 below details the liquid particle count of nitrile glove with coating and control glove without coating.
  • Table 31 below is ionic content extracted from nitrile gloves with and without coating.
  • Table 32 below details ESD properties of nitrile gloves with and without polyol coating.
  • the ionic anti-static coating compositions applied to nitrile gloves show greater ESD properties.
  • the ionic anti-static coatings are not suitable for use as a coating on a dipped article as they affected appearance and cleanliness of the gloves.
  • Addition of ionic component (potassium acetate) caused high concentration of potassium ion detected from Set 1 and Set 2 glove.
  • liquid particle extracted from Set 1 and Set 2 was higher compared to Control and Set 3. After the coating was dried, glossy and sticky patches were observed on the glove surface of Set 1 and Set 2. The glossy and sticky patches caused outer surface of the gloves stick to each other when the gloves were packed inside packaging material.
  • Gloves were prepared from the following composition set out below using standard elastomeric film production processes as known in the art.
  • Example 13 Addition of glycerine to the elastomeric composition
  • Example 14 Addition of different PEG'S to the elastomeric composition
  • Three gloves were prepared using the elastomeric composition defined above, with a control glove containing no polyol material, and two sample gloves containing different polyethylene glycols.
  • Set 1 contained 5 phr PEG 300, and set 2 contained 10 phr PEG 6000. These gloves were then tested for their surface resistivity.
  • Example 15 Addition of polyol material to the coagulant composition
  • Example 16 Polyol Material Added into Elastomeric Film-Forming Composition, Coagulant and/or Coating
  • ESD properties of gloves made using combinations of polyol material in the coagulant, polyol material in the elastomeric film forming composition and/or polyol material in the coatings are PEG 300.
  • An elastomeric article comprising:
  • polyol material selected from the group consisting of polyols, polyol esters and polyol derivatives
  • the elastomeric article has one or more of the following properties:
  • polysaccharides selected from the group consisting of: polyethylene glycols (PEG), polyethylene oxides (PEO), polypropylene glycols (PPG), monomeric diols, monomeric triols, sugars, sugar alcohols, and polysaccharides;
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • monomeric diols monomeric triols
  • sugars sugar alcohols
  • polysaccharides polysaccharides
  • a polyol ester selected from the group consisting of: PEG esters (including PEG fatty acid esters and PEG glycerol fatty acid esters, such as PEG oleate, PEG cocoate, PEG stearate, PEG acrylate, PEG glycerol cocoate, PEG 40-hydrogenated castor oil), glycerol esters (including glycerol stearate, glycerol oleate, glycol acrylate, polyglycerol esters of fatty acids) and sorbitan esters (such as sorbitan laurate, sorbitan stearate, sorbitan palmitic, and including polysorbates such as Polysorbate 20 and Polysorbate 80); or
  • a polyol derivative selected from the group consisting of: methoxypolyethylene glycol (MPEG), copolymers of ethylene oxide and propylene oxide, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • copolymers of ethylene oxide and propylene oxide glycol ethers
  • PEG ethers ethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol propoxylated ethylenediamine polyol
  • polyol material is: - a polyol selected from the group consisting of: polyethylene glycols (PEG) with an average molecular weight of between 200 and 20,000 g/mol, polyethylene oxides (PEO) with a molecular weight of between 20,000 and 10,000,000 g/mol, polypropylene glycols (PPG) with a molecular weight of between 300 and 4000 g/mol, monomeric diols containing between 2 and 12 carbon atoms, monomeric triols containing between 2 and 12 carbon atoms, sugars and sugar alcohols;
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • polyol ester selected from the group consisting of: PEG esters where the PEG has a molecular weight of between 200 and 20,000 g/mol, PEO esters where the PEO has a molecular weight of between 20,000 and 10,000,000 g/mol, PPG esters where the PPG has a molecular weight of between 300 and 4000 g/mol, glycerol esters and sorbitan esters, wherein the polyol ester preferably has an HLB of at least 5; or
  • a polyol derivative selected from the group consisting of: methoxypolyethylene glycol (MPEG) with a molecular weight between 350 and 750 g/mol, copolymers of ethylene oxide and propylene oxide with a molecular weight between 2000 and 5000 g/mol, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • PEG ethers polyethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol propoxylated ethylenediamine polyol
  • polyol material is a polyol selected from the group consisting of polyethylene glycols (PEG), polyethylene oxides (PEO), polypropylene glycols (PPG), monomeric diols, monomeric triols, sugars and sugar alcohols.
  • PEG polyethylene glycols
  • PEO polyethylene oxides
  • PPG polypropylene glycols
  • monomeric diols monomeric triols
  • sugars and sugar alcohols sugar alcohols
  • polyol material is a polyol with a hydroxyl number of at least 20, preferably more than 200 and more preferably more than 1000.
  • polyol material is a polyol ester selected from the group consisting of polyethylene glycol esters, glycerol esters and sorbitan esters, and the polyol ester comprises at least one -OH group, preferably between 1 -6 -OH groups, and an HLB of at least 5, and preferably between 8-18.
  • polyol material is a polyol derivative selected from the group consisting of methoxypolyethylene glycol (MPEG), copolymers of ethylene oxide and propylene oxide, glycol ethers, PEG ethers, ethylene glycol ether, propoxylated triethanolamine polyol, ethylene diamine polyether polyol and propoxylated ethylenediamine polyol.
  • MPEG methoxypolyethylene glycol
  • copolymers of ethylene oxide and propylene oxide glycol ethers
  • PEG ethers ethylene glycol ether
  • propoxylated triethanolamine polyol ethylene diamine polyether polyol
  • propoxylated ethylenediamine polyol 20.
  • elastomeric article of item 24 wherein the only elastomers in the elastomeric film are those selected from the group consisting of natural rubber, nitrile rubber, polyurethane, polyisoprene, polychloroprene, polystyrene, acrylic polymers, polybutadienes, and copolymers or blends of these polymers or their monomers.
  • 26. The elastomeric article of any one of items 1 to 25, in the form of a glove or finger cot.
  • the elastomeric article of item 26 having a modulus at 300% of up to 10 MPa (such as between 1 and 5 MPa), a stress at 500% of up to 15 Mpa, and/or an elongation to break of greater than or equal to 500% (such as between 500% and 1000%).
  • the elastomeric article of item 27 having a tensile strength of minimum 8 MPa and above, an elongation of between 600% and 1000% and/or a modulus at 300% of between 1 and 2.4 MPa.
  • the elastomeric article of item 27 or item 28 having an elongation that is at least 10% greater than that of the same article without said polyol material, and a modulus at
  • elastomeric article of any one of items 1 to 32 wherein the elastomeric article comprises a coating layer on a surface of the article, and the coating layer comprises said polyol material, and wherein the coating layer does not contribute to the total ionic content and/or liquid particle count measured according to IEST-RP-CC005.4.
  • a method of manufacturing an elastomeric article comprising an elastomeric film that has a surface resistivity of 10 11 ⁇ /sq or less and/or a tribo-electrical charge before rub of less than 50V and after rub of less than 300V and/or a static decay (from 1000V to 10V) of less than 1 second, the method comprising:
  • step (i) incorporating a polyol material into the coagulant composition used in step (a),
  • step (ii) incorporating a polyol material into the elastomeric film-forming composition used in step (b) and/or
  • step (iii) applying a coating composition comprising a polyol material to a surface of the elastomeric film produced in step (c),
  • polyol material is selected from the group consisting of polyols, polyol esters and polyol derivatives.
  • any one of items 35 to 37 comprising applying the coating composition by dipping the elastomeric film in the coating composition, tumble coating the coating composition onto the elastomeric film, spraying-coating the coating composition onto the elastomeric film, or soaking the elastomeric film in the coating composition.
  • the method of item 40 wherein the elastomeric article is an elastomeric glove or finger cot, and the method applies an about of 0.1 mL of coating composition per glove, preferably 0.5 to 5 mL per glove, or an equivalent amount per finger cot. 42.
  • the method of item 40 or item 41 wherein the tumble drying is continued for a time period of at least 5 minutes, preferably between 60 and 120 minutes, at a temperature of at least 35°C, and preferably between 50 and 70°C.
  • step (ii) of incorporating the polyol material into the elastomeric film-forming composition in an amount of between 0.01 and 60 phr, preferably between 0.01 and 30 phr.
  • the method of item 49 further comprising one or more hot washing steps comprising washing in hot deionised water or hot multi-filtered water at a temperature of between 40 and 80°C after the washing step, and/or spinning to remove water prior to the tumble drying step.
  • the method of item 53 further comprising one or more hot washing steps comprising washing in hot deionised water or hot multi-filtered water at a temperature of between 40 and 80°C after the washing step, and/or spinning to remove water prior to the tumble drying step.
  • the elastomeric film-forming composition comprises an elastomer selected from the group consisting of natural rubber, nitrile rubber, polyurethane, polyisoprene, polychloroprene, polystyrene, acrylic polymers, polybutadienes, and copolymers or blends of these polymers or their monomers.
  • a method for the manufacture of an elastomeric article comprising an elastomeric film that has a surface resistivity of 10 11 ⁇ /sq or less and/or a tribo-electrical charge before rub of less than 50V and after rub of less than 300V and/or a static decay (from 1000V to 10V) of less than 1 second, the method comprising applying a coating composition comprising a polyol material selected from the group consisting of polyols, polyol esters and polyol derivatives onto a surface of the elastomeric film.
  • any one of items 57 to 59 comprising applying the coating composition by dipping the elastomeric film in the coating composition, tumble coating the coating composition onto the elastomeric film, spray-coating the coating composition onto the elastomeric film, or soaking the elastomeric film in the coating composition.
  • the method of item 60 wherein the coating composition is applied by dipping, the method comprising dipping the elastomeric film into the coating composition containing from 0.1 % to 30% by weight of the polyol material, drying the coating composition to form a coating layer comprising the polyol material on the elastomeric film, and stripping the elastomeric film with the coating layer from the former to produce the elastomeric article.
  • the coating composition is applied by tumble coating or spray coating, the method comprising stripping the cured elastomeric film from the former after step (c), and tumbling elastomeric film stripped from the former in a tumble dryer in the presence of the coating composition.
  • elastomeric article is an elastomeric glove or finger cot
  • the method applies an about of 0.1 mL of coating composition per glove, preferably 0.5 to 5 mL per glove, or an equivalent amount per finger cot.
  • step (c) The method of item 60, wherein the coating composition is applied by soaking, the method comprising stripping the cured elastomeric film from the former after step (c), soaking the elastomeric film stripped from the former in the coating composition containing from 0.1 % to 30% by weight of the polyol material for a time period of at least 30 seconds, and preferably between 10 and 30 minutes, and drying the coating composition to form a coating layer comprising the polyol material on the elastomeric film.
  • elastomeric article is an elastomeric glove or finger cot
  • the method applies an amount of about of at least 0.1 mL of coating composition per glove, preferably 0.5 to 5 mL per glove, or an equivalent amount per finger cot.
  • any one of items 57 to 66, wherein the method comprises the application of an amount of coating composition such that the dried coating weight applied is at least 0.001 g per glove, preferably 0.005 to 1 g per glove, or an equivalent amount per finger cot.

Abstract

L'invention concerne des articles élastomères trempés ayant des propriétés de dissipation électrostatique (ESD) et des procédés pour leur fabrication. Les articles élastomères trempés comprennent un film élastomère et une couche de revêtement sur une surface de l'article, la couche de revêtement comprenant un matériau polyol choisi dans le groupe constitué par les polyols, les esters de polyol et les dérivés de polyol ; l'article élastomère ayant une résistivité de surface de 1011 Ω/sq ou moins. Les procédés de fabrication comprennent l'étape consistant à appliquer une composition de revêtement comprenant un matériau polyol choisi dans le groupe constitué de polyols, d'esters de polyol et de dérivés de polyol sur une surface d'un film élastomère.
PCT/AU2018/050976 2017-09-11 2018-09-10 Article élastomère synthétique et ses procédés de production WO2019046906A1 (fr)

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AU2018329205A AU2018329205B2 (en) 2017-09-11 2018-09-10 Synthetic elastomeric article and methods for producing thereof
CN201880069538.4A CN111542242B (zh) 2017-09-11 2018-09-10 合成弹性体制品及其制造方法

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AU2017903688 2017-09-11
AU2017903688A AU2017903688A0 (en) 2017-09-11 Synthetic Elastomeric Article and Methods for Producing Thereof

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CN111542242B (zh) 2023-10-20
AU2018329205A1 (en) 2020-03-26
AU2018329205B2 (en) 2023-03-02

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