WO2004044037A1 - Composition a base de latex synthetique - Google Patents

Composition a base de latex synthetique Download PDF

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Publication number
WO2004044037A1
WO2004044037A1 PCT/AU2003/001350 AU0301350W WO2004044037A1 WO 2004044037 A1 WO2004044037 A1 WO 2004044037A1 AU 0301350 W AU0301350 W AU 0301350W WO 2004044037 A1 WO2004044037 A1 WO 2004044037A1
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WO
WIPO (PCT)
Prior art keywords
latex
synthetic
carboxylated
staining
rubber article
Prior art date
Application number
PCT/AU2003/001350
Other languages
English (en)
Inventor
Kwong Ann Lew
Leslie Martin Barclay
Ah Kiew Wong
Sarala Devi Jayaraman
Original Assignee
Wrp Asia Pacific Sdn. Bhd.
Ip Organisers Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wrp Asia Pacific Sdn. Bhd., Ip Organisers Pty Ltd filed Critical Wrp Asia Pacific Sdn. Bhd.
Priority to AU2003269586A priority Critical patent/AU2003269586A1/en
Priority to JP2004550549A priority patent/JP2006505657A/ja
Priority to EP03750150A priority patent/EP1563000A1/fr
Publication of WO2004044037A1 publication Critical patent/WO2004044037A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber 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
    • 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
    • C08J2313/00—Characterised by the use of rubbers containing carboxyl groups

Definitions

  • the present invention relates to novel types of synthetic latex composition, which are identified as being suitable for producing non-staining dipped rubber articles such as a non-staining glove, condom, finger cot and balloon. More particularly, the invention relates to synthetic latex compositions, using synthetic carboxylated butadiene co-polymer latex containing only polyvalent metal chemical(s) for cross-linking, to produce non-staining rubber gloves.
  • the stains which are usually brown in colour, are usually observed when typical synthetic and natural rubber gloves are worn for as little as a few minutes.
  • the compositions described herein render the rubber articles, which are free from known allergens, which would normally cause allergic response in some individuals.
  • the applicable synthetic elastomer latices are synthetic carboxylated polymer latices, such as carboxylated acrylonitrile butadiene latex, carboxylated acrylic butadiene latex, carboxylated styrene butadiene latex, carboxylated chloro-butadiene latex or other carboxylated latex co-polymers of butadiene, which may be cross-linked, only using polyvalent metal chemicals, without the use of sulphur, sulphur containing accelerators, formaldehyde or unsaturated cross-linkable monomers.
  • carboxylated polymer latices such as carboxylated acrylonitrile butadiene latex, carboxylated acrylic butadiene latex, carboxylated styrene butadiene latex, carboxylated chloro-butadiene latex or other carboxylated latex co-polymers of butadiene, which may be cross-linked, only using polyvalent
  • the second, more common allergic reaction, Type IV is a contact reaction, caused by chemicals in the rubber, which can give rise to unpleasant skin reactions such as dermatitis.
  • the other, aesthetic problem, "copper staining" is very common, with all conventionally sulphur vulcanised natural and synthetic rubbers. It manifests itself by the gradual appearance of brown stains on the gloves, which give the effect of being soiled.
  • 2,662,874 discloses preparation of carboxyl containing polymers, which may be subsequently cross-linked by milling solid carboxylated polymer with polyvalent metal oxides such as those of zinc, magnesium, calcium, cadmium, titanium, aluminium, barium, strontium, copper, cobalt, tin, iron, lead and others, to produce dry rubber compounds.
  • polyvalent metal oxides such as those of zinc, magnesium, calcium, cadmium, titanium, aluminium, barium, strontium, copper, cobalt, tin, iron, lead and others.
  • UK Patent No. 785,631 discloses a process for the production of shaped articles from elastomeric polymers containing reactive groups. Included in this group of reactive polymers are polymers containing carboxyl groups, carbonyi groups, sulphonic acid groups, amide or basic groups, which may react with water-soluble salts or hydroxides of polyvalent metals, such as calcium chloride, barium chloride, magnesium chloride, zinc chloride, zinc sulphate, ferrous sulphate, barium hydroxide, calcium hydroxide, chromium acetate, chrome alum, copper acetate and aluminium salts.
  • polyvalent metals such as calcium chloride, barium chloride, magnesium chloride, zinc chloride, zinc sulphate, ferrous sulphate, barium hydroxide, calcium hydroxide, chromium acetate, chrome alum, copper acetate and aluminium salts.
  • 3,403,136 discloses the use of a cross-linking system for solid carboxylic elastomers, comprising of polyvalent metal oxides, combined with their corresponding peroxides, which prevents pre-cure of the polymer.
  • the preferred peroxides and oxides were those of Group II of the Periodic Table, in particular zinc, calcium and magnesium. This patent pertains to dry rubber compounds.
  • US Patent No. 3,976,723 discloses processes in which carboxyl containing acrylic polymers, in the solid form, are mixed with polyvalent metallic oxides in a mill or internal mixer prior to curing.
  • the polyvalent metallic oxides include those of zinc, magnesium, cadmium, calcium, titanium, aluminium, barium, strontium, copper, cobalt, tin and others, as well as polyvalent metallic hydroxides.
  • Japanese Patent No. 61-278546 discloses the use of metal oxides or hydroxides of zinc or magnesium for the cross-linking of carboxylated chloroprene rubber latex, used for foam rubber.
  • US Patent No. 4,525,517 discloses the use of one or more polyvalent metal oxides and one or more alkali metal salts (lithium, sodium or potassium) salts of C12-18 alkanoic acids, to mill with solid carboxylated nitrile rubber, so as to produce vulcanisable dry rubber compositions with improved scorch resistance.
  • alkali metal salts lithium, sodium or potassium
  • US Patent No. 5,014,362 discloses an elastomeric material to produce gloves having the ability to relax after initial stretching, such that the pressure on the hand is reduced. It describes the preferred material comprising a carboxylated nitrile butadiene rubber and containing a metallic compound, preferably oxides of lead, magnesium and zinc. The preferred oxide is zinc oxide, claimed at levels from 0.1 to 0.5 parts per 100 parts (phr) of nitrile butadiene rubber.
  • Example formulations in this patent also contain higher levels of sulphur (1.0 phr) and zinc dibutyl dithiocarbamate (1.Ophr).
  • nitrile latex carboxylated acrylonitrile butadiene latex
  • nitrile latex carboxylated acrylonitrile butadiene latex
  • One mechanism is via sulphur cross- linking between the diene sections of molecules of the polymer and the other cross-links are due to ionic bonding formed by reaction between carboxyl groups in the nitrile polymer and metal oxides. Consequently, all the manufacturers of nitrile latex provide guideline formulations, which contain both sulphur and thio accelerators, together with zinc oxide.
  • a process for preparing a synthetic latex compound includes the steps of a) adding a polyvalent metal chemical or a mixture thereof, to a surfactant stabilised synthetic carboxylated latex, or blend with other synthetic latex, to form a synthetic latex compound, b) stirring the synthetic latex compound, c) diluting the synthetic latex compound obtained in step (b) to a predetermined total solid content (TSC) and d) maintaining the synthetic latex compound obtained in step (c) at a temperature between 0 to 80°C.
  • TSC total solid content
  • a synthetic latex compound obtained from a process which includes the steps of a) adding a polyvalent metal chemical or a mixture thereof to a surfactant stabilised synthetic carboxylated latex, or blend with other synthetic carboxylated or non-carboxylated latex or latices to form a synthetic latex compound, b) stirring the synthetic latex compound, c) diluting the synthetic latex compound obtained in step (b) to a predetermined total solid content (TSC) and d) maintaining the synthetic latex compound obtained in step
  • TSC total solid content
  • non-staining dipped rubber articles such as a non-staining glove, condom, finger cot or balloon made from composition containing an effective amount of synthetic carboxylated butadiene co-polymer latex and an effective amount of polyvalent metal chemical or mixture thereof as the sole cross-linking agent.
  • non-staining dipped rubber articles such as a non- staining rubber article such as glove, condom, finger cot or balloon made from a composition containing an effective amount of synthetic polymer latex or latices, an effective amount of synthetic carboxylated butadiene co-polymer latex and an effective amount of polyvalent metal chemical as the sole cross-linking agent.
  • Figure 1 shows the effect of the level of zinc oxide on the tensile properties of gloves, using a commercially available carboxylated nitrile latex.
  • Figure 2 shows the different physical properties attained when using a number of commercially available carboxylated nitrile latices, from different manufacturers, using the same base formulation.
  • the present invention relates to processes for producing non-staining dipped rubber articles such as a non-staining glove, condom, finger cot and balloon from synthetic latex and a latex composition for producing the same. More particularly, the invention relates to processes for producing a non-staining glove made from synthetic elastomeric compositions, which are free from the common problem of unsightly brown stains, which are usually observed when typical synthetic and natural rubber gloves are worn for as little as a few minutes and a novel synthetic latex composition for producing non-staining rubber articles such as a non-staining glove, condom, finger cot and balloon.
  • the invention as described hereinafter, describes processes for producing non- staining gloves, which are free from some if not all of the above-mentioned problems.
  • the gloves may be produced from carboxylated synthetic copolymers of butadiene, including carboxylated acrylonitrile butadiene latex, carboxylated acrylic butadiene latex, carboxylated chloroprene latex and other carboxylated synthetic polymers.
  • the preferred synthetic latex is carboxylated acrylonitrile butadiene latex and the inventors have evaluated most of the nitrile latices available commercially.
  • the inventors have established that this technology can be applied to all, but their evaluations have shown that all nitrile latices, even those having the similar levels of acrylonitrile/butadiene/carboxylic acid levels, can exhibit markedly different physical properties in the same formulation.
  • the sole cross-linking mechanism employed utilises ionic bonding between polyvalent metal ions and the carboxylate groups of the elastomer.
  • the preferred sources of polyvalent metal ions are zinc oxide, zinc carbonate and calcium carbonate or any combinations of these, although the inventors have established that other sources such as magnesium oxide, magnesium carbonate, hydroxides of calcium, magnesium, aluminium and also aluminates, can be effective to give sufficient cross-linking.
  • the process employed in the production of gloves, utilising this technology is the typical process used in current manufacture of unsupported gloves of thickness, typically 0.1 to 0.2 mm thick.
  • the latex compound is produced in conventional latex compounding mixing tanks, by adding pre-dispersed zinc oxide or other source of polyvalent metal, to a surfactant stabilised synthetic carboxylated latex, such as nitrile latex.
  • the latex compound would normally be stirred for several hours and then diluted to the normal TSC required for a particular glove dipping line.
  • the normal TSC would be in the range 25 to 35% and the latex would be maintained at a temperature of about 25 Q C.
  • the dipping process used is that of a coagulant dipping process and the coagulant normally used is aqueous or aqueous/alcohol solutions of calcium nitrate, calcium chloride or mixture of the two, at concentrations from 10% to 30%.
  • a suitable mould release additive in the case of powder-free coagulants
  • a powder coagulant may be used for powdered gloves.
  • the glove formers are dried at temperatures in the range 70 to 100 Q C and then cooled to about 50 S C. The formers then dip into the latex compound and, after partial drying, the latex-coated formers are leached in water at about 45 9 C.
  • the gloves may then be further processed by different methods, and three examples are given.
  • the gloves on the formers would then be dipped into a selected polymer dispersion, followed by beading.
  • the formers would then enter the cure/drying oven, where the films are subjected to temperatures 100 to 120 S C for up to 40 minutes. This is followed by leaching in water at about 70 Q C, dried at about 100 S C and finally cooled before stripping the polymer coated gloves from the formers.
  • the gloves In the case of on-line chlorination, the gloves would be beaded after the pre-cure leach, then cured as above. This would then be followed by an on-line chlorination process, leaching, drying and finally, cooling before stripping.
  • the third option would be to utilise a powder coagulant system followed by a powder slurry after curing and then process the gloves off-line, either by chlorination or a suitable anti-tack process for powder-free gloves. If powdered gloves are required, there is no need for any off-line processing.
  • the invention as described hereinafter relates to the development of simple formulations, using only polyvalent metal chemicals as the sole system for cross-linking synthetic carboxylated butadiene co-polymer type elastomers, to produce articles such as gloves, which are non-staining and possess the required tensile properties for medical gloves. It is commonly considered that sulphur and sulphur containing accelerators are essential in combination with polyvalent metal chemicals to compound with synthetic carboxylated butadiene co-polymer type latices in order to produce rubber articles such as gloves, which meet the tensile properties for various worldwide regulatory organisations such as ASTM and EN.
  • the formulations described in this invention do not contain any cross- linkable monomers, which could also be utilised to make non-staining rubber articles.
  • the staining referred to is usually readily observed when the typical synthetic and natural rubber gloves are worn for as little as a few minutes. It is due to reaction between the sulphur-containing chemicals used as accelerators and traces of metals such as copper, silver, lead, nickel or other reactive metals, when the wearers hands contact objects such as coins, keys, handles, etc.
  • the said latex compound is prepared in conventional latex compound mixing tanks.
  • the polyvalent metal chemical or chemicals are normally added in a liquid form, either as an aqueous dispersion or aqueous solution to a surfactant stabilised synthetic carboxylated latex in a stirred mixing tank.
  • Other materials are normally added, such as alkali, for pH adjustment and pigment, for a desired colour.
  • the latex compound is then normally diluted with demineralised water to attain a desired Total Solids Content (TSC) and the stirred compound is usually maintained at a temperature in the range 20 to 30 9 C, although temperatures up to 80 S C or as low as 0 Q C may be used.
  • TSC Total Solids Content
  • the latex compound may be transferred to the latex dip tank on a conventional dipping machine for dipped rubber goods.
  • Figure 1 shows the effect of the level of zinc oxide on the tensile properties of gloves, using a commercially available carboxylated nitrile latex. It shows clearly that the tensile strength increases steadily, with increased levels of zinc oxide, together with increase in 300% modulus and a steady decrease in Elongation at Break (shown as the end of each curve).
  • Figure 2 demonstrates the different physical properties attained when using a number of commercially available carboxylated nitrile latices, from different manufacturers, using same base formulation. However, as mentioned earlier, it is possible to attain the desired physical properties by adjustments to the formulation for each type of synthetic carboxylated latex.
  • Figure 3 illustrates the typical manufacturing processes for the production of dipped rubber articles, in particular, rubber gloves.
  • the process includes the steps of: a) starting at the "former cleaning" stage, where the rubber article formers are cleaned by immersion in cleaning fluids, combined with mechanical brushing, b) the clean formers are dried in an oven at temperatures in the range 70 to 100 Q C, c) the formers are cooled to a temperature in the range 50 to 70 9 C, d) the formers may either dip into a powder coagulant (Path 1), or into a powder-free coagulant (Path 2).
  • the coagulant normally contains an aqueous, aqueous/alcohol or alcohol solution of a calcium salt plus wetting agent and powder or a powder-free material as a "release agent", e) the coagulant coated former is dried in an oven at a temperature in the range 70 to 100 9 C, f) the coagulant coated former is cooled to a temperature of 40 to 60 9 C, g) the coagulant coated former is dipped into the latex compound which is maintained at a temperature in the range 20 to 30 9 C, h) the latex compound coating on the former is then partially dried at a temperature in the range 30 to 70 9 C, i) the partially dried film on the former is leached in water or an aqueous solution at a temperature in the range 30 to 50 9 C, j) the leached film on the former may then dip into a polymer dispersion (Path 3) or by-pass the polymer tank (Path 4), k) the rubber article is beaded, I) the rubber article on
  • Rubber articles from the various flow paths described above may be used to make various versions of rubber articles.
  • the options are powdered gloves, off-line chlorinated gloves, off-line anti-tack processed gloves, outer powdered/inner polymer-coated gloves, off-line chlorinated/polymer coated powder-free gloves, off-line processed polymer- coated powder-free gloves, outer powdered/inner on-line chlorinated gloves, outer powder-free/inner on-line chlorinated powder-free gloves, off-line chlorinated/on-line chlorinated powder-free gloves, off-line anti-tack/on-line chlorinated powder-free gloves and powder-free polymer-coated gloves.
  • the manufacturing process from the flow diagram follows Paths 1 , 4, 5 and 7 and then the gloves are dried, cooled and packed.
  • the powdered gloves are processed in an off-line chlorinator, dried, cooled and packed.
  • the powdered gloves are processed in a machine using an anti-tack additive, dried, cooled and packed.
  • the manufacturing process from the flow diagram follows Paths 1 , 3, 5 and 8 and then the gloves are dried, cooled and packed.
  • the outer powdered/inner polymer-coated gloves are processed in an off-line chlorinator, dried, cooled and packed.
  • the outer powdered/inner polymer-coated gloves are processed in a machine using an anti-tack additive, dried, cooled and packed.
  • the manufacturing process, from the flow diagram follows Paths 1 , 4, and 6 and then the gloves are dried, cooled and packed.
  • the manufacturing process, from the flow diagram follows Paths 2, 4 and 6 then dried, cooled and packed.
  • the outer powdered/inner on-line chlorinated gloves are subjected to an off-line chlorination process in order to chlorinate the outer surface of the gloves and then the gloves are dried, cooled and packed.
  • the outer powdered/inner on-line chlorinated gloves are processed in a machine using an anti-tack additive, dried, cooled and packed .
  • the manufacturing process from the flow diagram, follows Paths 2, 3, 5 and 8 and then the gloves are dried, cooled and packed. These gloves may also be further processed off-line for enhanced surface properties.
  • carboxylated nitrile latex For the purpose of this specification, one commercially available carboxylated nitrile latex was selected, compounded to a formulation (as shown in Table 1) and processed to produce powder-free nitrile gloves, free from known allergens and staining, with a tensile strength at break of 18 to 20 Mpa, a 300% Modulus of less than 2.0 Mpa and Elongation at break in excess of 750%.
  • the same films show minimal change in these tensile properties after ageing for 7 days at 70 9 C, as shown in the data in Table 2.
  • the present inventors' evaluations on formulations containing levels of zinc oxide up to 2.5 phr were conducted using different sources of nitrile latex and the relaxation properties were such that all retained less than 10% of original stress after 6 minutes at 100% elongation.
  • relaxation studies were conducted on a number of different nitrile latex films, without the presence of cross-linking agents such as polyvalent metal chemicals, sulphur vulcanisation chemicals or reactive monomers, which were dipped by multiple "straight dips", to avoid any cross-linking by the polyvalent metal calcium ions of the coagulant system. These films were subjected to stretching to 100% to measure relaxation properties and the relaxation properties were also found to be the same as those above.
  • the above formulation was stirred gently overnight and the total solids content adjusted to 30%.
  • Formers were cleaned on-line, using propriety cleaning chemicals, which after passing through a rinse water tank, were dried in an oven at about 80 9 C.
  • the formers then dipped into a coagulant containing 25% calcium nitrate and a stearate-based release agent.
  • the coagulant coated formers were then dried at a temperature in the range 70 to 100 9 C, followed by cooling to about 50 9 C.
  • the coagulant coated formers were then dipped into the latex compound with a dwell time of 10 seconds.
  • the latex compound coated formers then passed through a gelling oven at 60 9 C, followed by leaching in water at 45 9 C for 2 minutes and then beading.
  • the gloves on the formers were then cured/dried in an oven with temperatures up to 120 9 C for 30 minutes.
  • the emerging gloves were cooled in a water bath and then entered an on-line chlorination process, followed by final drying, cooling and stripping.
  • Table 4 shows typical properties of the gloves from this process.
  • a carboxylated acrylic butadiene co-polymer latex was compounded with various additives as in Table 5 below. TABLE 5

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Gloves (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention a trait à une composition à base d'un composé au latex synthétique, qui est destinée à produire des articles en caoutchouc non tachants fabriqués par trempage, tels que des gants, des préservatifs, des doigtiers et des ballonnets non tachants. Ladite composition contient un caoutchouc acrylonitrile butadiène carboxylé synthétique ou un caoutchouc copolymère de butadiène carboxylé synthétique, exempt de tout soufre ou de tout accélérateur ou substance chimique contenant du soufre. Le seul système de réticulation utilisé est composé uniquement de substances chimiques métalliques polyvalentes, ce qui permet d'empêcher le maculage au cuivre ou à d'autres métaux lourds des articles en caoutchouc, et d'éliminer également les allergènes de type I et de type IV.
PCT/AU2003/001350 2002-11-11 2003-10-13 Composition a base de latex synthetique WO2004044037A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003269586A AU2003269586A1 (en) 2002-11-11 2003-10-13 A synthetic latex composition
JP2004550549A JP2006505657A (ja) 2002-11-11 2003-10-13 合成ラテックス組成物
EP03750150A EP1563000A1 (fr) 2002-11-11 2003-10-13 Composition a base de latex synthetique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20024206 2002-11-11
MYPI20024206 2002-11-11

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WO2004044037A1 true WO2004044037A1 (fr) 2004-05-27

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PCT/AU2003/001350 WO2004044037A1 (fr) 2002-11-11 2003-10-13 Composition a base de latex synthetique

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EP (1) EP1563000A1 (fr)
JP (1) JP2006505657A (fr)
AU (1) AU2003269586A1 (fr)
WO (1) WO2004044037A1 (fr)

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WO2008107914A2 (fr) * 2007-03-06 2008-09-12 Paradise Rubber Industries Vessie stratifiée sans couture en latex acrylonitrile butadiène carboxyle et son procédé de fabrication
WO2011068394A1 (fr) 2009-12-01 2011-06-09 Kossan Sdn Bhd Caoutchouc élastomère et produits en caoutchouc sans emploi d'accélérateurs de vulcanisation ni de soufre
US8118969B2 (en) 2006-11-30 2012-02-21 Illinois Tool Works Inc. Water-based polychloroprene adhesive
WO2015006808A1 (fr) * 2013-07-16 2015-01-22 Skinprotect Corporation Sdn Bhd Compositions de formation de film élastomère et articles fabriqués à partir du film élastomère
US9085100B2 (en) 2009-02-05 2015-07-21 Diptech Pte Limited Production of elastomeric films
EP2622976A4 (fr) * 2010-09-30 2016-09-28 Kossan Sdn Bhd Gant de caoutchouc élastomère dépourvu de soufre et comprenant un accélérateur de vulcanisation, destiné à des salles blanches
WO2018119490A1 (fr) * 2016-12-30 2018-07-05 Skinprotect Corporation Sdn Bhd Compositions élastomères filmogènes et articles et procédés associés
US10023718B2 (en) 2016-07-12 2018-07-17 Twolink Sdn Bhd Accelerator free and high filler load nitrile glove
EP3412717A4 (fr) * 2016-09-01 2019-05-08 LG Chem, Ltd. Composition de latex pour moulage par immersion, et article moulé préparé à partir de celle-ci
WO2019197520A1 (fr) 2018-04-11 2019-10-17 Omya International Ag Composition de carbonate de calcium comprenant une composition pour préparation de film élastomère
US10626283B2 (en) 2013-11-19 2020-04-21 Ansell Limited Polymer blends of nitrile rubber and polychloroprene
US10731013B2 (en) 2016-01-29 2020-08-04 Skinprotect Corporation Sdn Bhd Elastomeric articles, compositions, and methods for their production
US11284656B2 (en) 2017-07-25 2022-03-29 Skinprotect Corporation Sdn Bhd Elastomeric gloves and methods for their production
US20220205907A1 (en) * 2020-06-08 2022-06-30 Alison S. Bagwell Method for determining residual carbamate compounds on an elastomeric article

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MY147739A (en) * 2005-07-20 2013-01-15 Diptech Pte Ltd Elastomeric films and gloves
NL2006847C2 (en) * 2011-05-25 2012-11-27 Budev Bv Method for treatment of natural rubber latex and/or synthetic rubber products, a system for treatment and the resulting rubber products.
MY163265A (en) * 2014-11-06 2017-08-21 Top Glove Sdn Bhd Latex formulation for making elastomeric products
MY181463A (en) * 2015-12-30 2020-12-22 Top Glove Int Shd Bhd Nitrile rubber article
MY198073A (en) * 2019-11-07 2023-07-31 Kossan Sdn Bhd Polymeric/inorganic composite particle formulation and methods of producing rubber articles using said formulation

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CN105492179A (zh) * 2013-07-16 2016-04-13 皮肤防护有限公司 形成弹性体膜的组合物和由弹性体膜制成的制品
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AU2014292805C1 (en) * 2013-07-16 2018-06-14 Skinprotect Corporation Sdn Bhd Elastomeric film-forming compositions and articles made from the elastomeric film
WO2015006808A1 (fr) * 2013-07-16 2015-01-22 Skinprotect Corporation Sdn Bhd Compositions de formation de film élastomère et articles fabriqués à partir du film élastomère
WO2015006806A1 (fr) * 2013-07-16 2015-01-22 Skinprotect Corporation Sdn Bhd Compositions élastomères filmogènes et articles faits de ce film élastomère
AU2014292805B9 (en) * 2013-07-16 2017-07-20 Skinprotect Corporation Sdn Bhd Elastomeric film-forming compositions and articles made from the elastomeric film
US10377893B2 (en) 2013-07-16 2019-08-13 Skinprotect Corporation Sdn Bhd Elastomeric film-forming compositions and articles made from the elastomeric film
US10626283B2 (en) 2013-11-19 2020-04-21 Ansell Limited Polymer blends of nitrile rubber and polychloroprene
US10731013B2 (en) 2016-01-29 2020-08-04 Skinprotect Corporation Sdn Bhd Elastomeric articles, compositions, and methods for their production
US11725085B2 (en) 2016-01-29 2023-08-15 Skinprotect Corporation Sdn Bhd Elastomeric articles, compositions, and methods for their production
US10023718B2 (en) 2016-07-12 2018-07-17 Twolink Sdn Bhd Accelerator free and high filler load nitrile glove
EP3412717A4 (fr) * 2016-09-01 2019-05-08 LG Chem, Ltd. Composition de latex pour moulage par immersion, et article moulé préparé à partir de celle-ci
US10927240B2 (en) 2016-09-01 2021-02-23 Lg Chem, Ltd. Latex composition for dip-molding, and molded article prepared from same
WO2018119490A1 (fr) * 2016-12-30 2018-07-05 Skinprotect Corporation Sdn Bhd Compositions élastomères filmogènes et articles et procédés associés
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