EP0809565A4 - Acrylemulsionsbeschichtungen für gummigegenstände - Google Patents

Acrylemulsionsbeschichtungen für gummigegenstände

Info

Publication number
EP0809565A4
EP0809565A4 EP96906380A EP96906380A EP0809565A4 EP 0809565 A4 EP0809565 A4 EP 0809565A4 EP 96906380 A EP96906380 A EP 96906380A EP 96906380 A EP96906380 A EP 96906380A EP 0809565 A4 EP0809565 A4 EP 0809565A4
Authority
EP
European Patent Office
Prior art keywords
acrylic based
copolymer
emulsion copolymer
based emulsion
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96906380A
Other languages
English (en)
French (fr)
Other versions
EP0809565A1 (de
Inventor
Ivan Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avery Dennison Corp
Original Assignee
Avery Dennison Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/388,030 external-priority patent/US5691069A/en
Priority claimed from US08/486,947 external-priority patent/US5700585A/en
Application filed by Avery Dennison Corp filed Critical Avery Dennison Corp
Publication of EP0809565A1 publication Critical patent/EP0809565A1/de
Publication of EP0809565A4 publication Critical patent/EP0809565A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • Water leaching may and usually is employed as part of the procedure to remove rubber impurities.
  • the methods and materials of glove manufacture are also described, for instance, in
  • Halogenation e.g. chlorination
  • other chemical surface treatments have been used to eliminate the need for a powder coat on the final product to enable dry donning. While effective, this step is expensive and has the shortcoming of reducing shelf life of the rubber article. It would be desirable to provide a rubber article with a powder-free donning surface without resorting to the expensive and article deteriorating practices now in vogue. This could substantially reduce the cost of manufacture and maximize the shelf life of the rubber article.
  • U.S. Patent 4,304,008 applies a covalently bonded silicone or urethane to the outer surface of the glove and halogenates the inner surface.
  • the halogenated inner surface eliminates the need for a donning powder.
  • U.S. Patent 4,310,928, also to Joung and incorporated herein by reference teaches the deposition of a lipo compound (lipid or lipophilic substances) in place of a powder of mineral origin in combination with a surfactant in a coagulant solution to form a uniform film on a glove mold onto which the rubber is coagulated.
  • the lipo compound and surfactant enable stripping of a formed glove from its mold.
  • the acrylic based copolymers are preferably emulsion based copolymers of at least one reactive low surface energy monomer, preferably a silicone oligomer, at least one alkyl acrylate and at least one reactive hard monomer, the total of hard monomers being present in an amount sufficient to form a non-tacky copolymer directly or by blending of copolymers.
  • the copolymers exhibited at least one dominant glass transition temperature (Tg) peak above O°C and typically at least one dominant glass transition temperature peak below about O°C.
  • Tg dominant glass transition temperature
  • One effective glass transition temperature is generally above about 15°C, preferably from about 15 to about 60°C. It is presently preferred that at least the donning surface be formed by sequential polymerization of two monomer systems; one providing the dominant low glass transition temperature peak, the other providing the dominant high glass transition temperature peak.
  • the coagulant may be deposited on the acrylic based copolymer or deposited therewith from suspension.
  • the object is to provide a surface concentration of coagulant salt which will enable coagulation of the latex onto the deposited copolymer coat in a commercially acceptable time.
  • the preferred coagulant salt is calcium nitrate and is used in a concentration up to about 40, preferably from about 20 to about 40 percent by weight of the suspension.
  • the mold having a coagulant and polymer coated surface is immersed into a rubber emulsion or latex from which the rubber deposits and coagulates on the surface of the copolymer forming a coated interior glove surface.
  • the formed rubber article is dried, cured, then immersed into an aqueous suspension of the same or a different acrylic based copolymer which exhibits good donning characteristics. Dipping forms a donning polymer coat on the exterior of the rubber glove.
  • the formed coated glove is then stripped from the mold. This reverses the glove placing the donning coat on the interior of the glove.
  • water leaching may be effectively employed for rubber purification.
  • the preferred mold is a contoured mold.
  • molds having a textured to highly polished ceramic or porcelain surface and molds having a fluorocarbon coating may be employed, it is preferred to employ a mold which is sufficiently textured to produce a dull finish in the deposited laminate formed by depositing the rubber from the latex onto the copolymer coating. This is achieved by roughening the mold surface by blasting with sand or glass beads. The surfaces used have been measured to have a roughness of from about 8 to 10 microns peak to valley.
  • FIG. 1 is a flow diagram of the current method of rubber glove manufacture
  • the monomers are also selected to provide sufficient elongation so that the acrylic based copolymer coating will stretch or elongate with the rubber with minimal cracking, flaking or debonding.
  • Suitable copolymers have an elongation of 100 to 500% or more, typically from about 100 to about 300% when self bonded to a rubber surface.
  • the articles and surgeons which have the most critical requirements are examination and surgeons gloves. Because of their complex shape, they must be capable of being stripped from a mold using commercially acceptable practices and yet provide, a surface, which when stripped from the mold, has good tactile feel; that is, the ability of a person to pick up articles with a good grip. In this regard, good tactile feel is contra to good mold stripping.
  • One class of the monomers used in forming the copolymers are alkyl acrylate monomers containing from 1 to about 10 carbon atoms in the alkyl group, present in a total amount of from about 30 to about 85% by weight of the monomers, preferably from about
  • the alkyl acrylate monomers that may be used include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, and the like.
  • the presently preferred alkyl acrylate monomers are butyl acrylate and methyl acrylate.
  • FIG. 3 is a glass transition temperature plot for a good donning copolymer coating where relative peak intensities of glass transition temperature are reversed.
  • weight ratio of the soft or low glass transition temperature copolymer to high glass transition temperature copolymer be in the range of about 1: 1 , to about 1:3, preferably about 1 to 1.5.
  • the suspension formed from the emulsion copolymer tolerate electrolytes typically employed for latex coagulation in concentration typically used for latex coagulation, i.e., in the range of about 3 to about 10% by weight of suspension.
  • the presently preferred surfactant system is a combination of anionic surfactants.
  • One of the anionic surfactants has a molecular formula C 2O H 37 0 7 NaS and containing 20 mols of ethylene oxide and is used in admixture with anionic surfactants which are salts of sulfated nonyl phenoxypoly (ethyleneoxy) ethanol and sodium lauryl ether sulfate.
  • Vinyl-addition silicone systems react by thermally induced addition-cure (hydrosilation) between polydimethyl-hydrogen siloxane crosslinkers and reactive vinyl-functional silicone polymers to furnish a cured polymer.
  • a coagulant salt is required to cause the rubber to deposit from its emulsion (latex) onto a surface of the polymer.
  • the coagulant may be applied after drying of the copolymer on the surface of the mold, a considerable savings in time and cost can be realized by combining a coagulant with the copolymer suspension. It has surprisingly been found that the copolymer suspensions of the instant invention can tolerate the high amount of polyvalent O 96/25278 PCMJS96/01866
  • the presently preferred molds are smooth contoured molds having a textured, or smooth ceramic, porcelain or a fluorocarbon surface which will accept the coating of the copolymer or the copolymer and coagulant and release the formed rubber article at the completion of the process.
  • the amount of time of immersion in the rubber emulsion determines the thickness of the formed rubber coat.
  • a typical thickness is from about 6 to about 10 mils.
  • FIG. 3 shows the DSC profile for the copolymer with major glass transitive temperature peaks at -21.04°C, 11.74°C + 12.45 and -l-28.55 c C. Surface morphology revealed a slightly irregular continuous surface with microcraters and submicron protrusions, the microcrater diameters ranging from 0.1 to 1 ⁇ .
  • FIG. 4 shows the DSC plot for this polymer and the several glass transition peaks, the major ones being at -12.51 °C, 13.57°C and 29.76°C.
  • the second monomer charge there was employed a monomer mix of 348 parts styrene, 136.6 parts butyl acrylate, 9 parts methylacrylic acid, 248 parts acrylic acid, 30.8 parts RC 726, 8.7 parts N-isobutoxymethyl acrylamide, the incremental catalyst solution contained 70.5 parts deionized water, and 2.5 parts of potassium persulfate. There was formed by sequential emulation polymerization emulsion of the copolymers which a total solid content of 53.3. The formed copolymers provided aggressive protective coatings for rubber surfaces.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Gloves (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
EP96906380A 1995-02-14 1996-02-12 Acrylemulsionsbeschichtungen für gummigegenstände Withdrawn EP0809565A4 (de)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US38957195A 1995-02-14 1995-02-14
US08/388,030 US5691069A (en) 1995-02-14 1995-02-14 Acrylic emulsion coatings for rubber articles
US388030 1995-02-14
US389571 1995-02-14
US48671095A 1995-06-07 1995-06-07
US08/486,947 US5700585A (en) 1995-02-14 1995-06-07 Acrylic emulsion coatings for formed articles
US486710 1995-06-07
US486947 1995-06-07
US08/486,948 US5712346A (en) 1995-02-14 1995-06-07 Acrylic emulsion coatings
US486948 1995-06-07
PCT/US1996/001866 WO1996025278A1 (en) 1995-02-14 1996-02-12 Acrylic emulsion coatings for rubber articles

Publications (2)

Publication Number Publication Date
EP0809565A1 EP0809565A1 (de) 1997-12-03
EP0809565A4 true EP0809565A4 (de) 1998-05-06

Family

ID=27541414

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96906380A Withdrawn EP0809565A4 (de) 1995-02-14 1996-02-12 Acrylemulsionsbeschichtungen für gummigegenstände

Country Status (8)

Country Link
EP (1) EP0809565A4 (de)
JP (1) JPH11507085A (de)
CN (1) CN1078123C (de)
AU (1) AU710920B2 (de)
CA (1) CA2212861A1 (de)
ID (1) ID23598A (de)
IL (1) IL117123A (de)
WO (1) WO1996025278A1 (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284856B1 (en) * 1995-02-14 2001-09-04 Avery Dennison Corporation Acrylate, silicone, styrene, urethane copolymer coatings for natural and synthetic rubber articles
WO1999030888A1 (de) * 1997-12-17 1999-06-24 Münch Chemie Labor Gmbh Vorrichtung und verfahren zur herstellung von puderfreien, proteinarmen tauchartikeln, insbesondere von operations- und untersuchungshandschuhen
KR100499958B1 (ko) * 1999-01-22 2005-07-11 에스케이씨 주식회사 이미지 수용층용 조성물 및 이로부터 형성된 이미지수용층을 구비한 고분자 필름
US6576337B1 (en) 1999-07-28 2003-06-10 Precision Dippings Marketing Limited Rubber articles adapted to make weldable seals; their manufacture and use
JP2004523389A (ja) * 2001-02-21 2004-08-05 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション パウダーフリー天然又は合成ゴム製品のための離型及び不粘着性被覆剤
US20030118761A1 (en) 2001-12-21 2003-06-26 Kimberly-Clark Worldwide, Inc. Elastomeric articles having improved chemical resistance
US6790933B2 (en) 2002-08-16 2004-09-14 Kimberly-Clark Worldwide, Inc. Low protein natural latex articles
US6872761B2 (en) * 2003-04-24 2005-03-29 Henkel Kommanditgesellschaft Auf Aktien Compositions for acoustic-damping coatings
US7052642B2 (en) 2003-06-11 2006-05-30 Kimberly-Clark Worldwide, Inc. Composition for forming an elastomeric article
US7767251B2 (en) * 2005-03-16 2010-08-03 Shiping Wang Repellent elastomeric article
CL2007003131A1 (es) 2006-11-01 2008-07-04 Lucite Int Inc Metodo para fabricar un articulo que comprende formular composicion acrilica que tiene un agente de transferencia con grupo que reacciona con isocianato y luego unir a una composicion que contiene isocianato; articulo; metodo que mejora la eficiencia
CN110194815B (zh) 2013-10-29 2022-12-30 阿利吉安斯公司 亲水/疏水的水性聚合物乳液和与其相关的产品和方法
TWI609640B (zh) * 2016-07-12 2018-01-01 帝藝國際貿易股份有限公司 用於製備手套之組合物及利用其製備手套之方法
MX2019011235A (es) * 2017-03-23 2019-11-01 Neos Kk Agente de tratamiento de superficie y metodo para producirlo.
CN114276729A (zh) * 2020-09-17 2022-04-05 顶级手套国际有限公司 一种用于涂覆弹性体制品的无硅聚合物涂料组合物及制备其涂覆的弹性体制品的方法
CN112592433A (zh) * 2020-11-27 2021-04-02 擎天材料科技有限公司 水性丙烯酸树脂、涂料组合物及其应用

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US2795564A (en) * 1953-05-13 1957-06-11 Rohm & Haas Aqueous paint bases and water-base paints and process for preparing them
US3255492A (en) * 1961-05-31 1966-06-14 Galen Entpr Inc Form for casting seamless, ambidextrous plastic gloves
FR2272156A2 (en) * 1974-05-21 1975-12-19 Du Pont Aqueous coating compsn. for flexible substrates - contg. acrylic resin based on four monomers and alkylated melamine-formaldehyde resin
US4027060A (en) * 1973-10-12 1977-05-31 Sutures, Inc. Rubber articles having improved slip coatings
US4082862A (en) * 1975-06-24 1978-04-04 Sutures Inc. Process for the production of rubber articles having improved slip coating
US4680335A (en) * 1985-03-20 1987-07-14 Courtaulds Plc Polymer compositions
WO1991005657A1 (en) * 1989-10-18 1991-05-02 Bioresearch, Inc. Articles having improved slip coatings
US5202368A (en) * 1989-01-31 1993-04-13 Ici Australia Operations Proprietary Limited Silicone coating compositions
EP0544569A1 (de) * 1991-11-27 1993-06-02 Rhone-Poulenc Chimie Wässrige Polymerdispersionen aus Styrol/carboxylierten Acrylat-Polymeren und ihre Verwendung als Bindemittel in Klebstoff- und Lackzusammensetzungen
JPH05310857A (ja) * 1992-05-05 1993-11-22 Showa Highpolymer Co Ltd 水性撥水加工用コーティング剤
WO1995029196A1 (en) * 1994-04-20 1995-11-02 Asahi Kasei Kogyo Kabushiki Kaisha Water-base silicone-modified acrylate polymer emulsion
WO1996025279A1 (en) * 1995-02-14 1996-08-22 Allegiance Corporation A multiple dip process for making a powder-free article
US5661208A (en) * 1995-08-11 1997-08-26 Dow Corning Corporation Rubber and vinyl protectant

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US5214095A (en) * 1988-07-07 1993-05-25 Rohm And Haas Company Stable aqueous emulsion copolymers with siloxane functionality
US5084514A (en) * 1990-11-14 1992-01-28 Reichhold Chemicals, Inc. Latex gloves with improved donnability

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795564A (en) * 1953-05-13 1957-06-11 Rohm & Haas Aqueous paint bases and water-base paints and process for preparing them
US3255492A (en) * 1961-05-31 1966-06-14 Galen Entpr Inc Form for casting seamless, ambidextrous plastic gloves
US4027060A (en) * 1973-10-12 1977-05-31 Sutures, Inc. Rubber articles having improved slip coatings
FR2272156A2 (en) * 1974-05-21 1975-12-19 Du Pont Aqueous coating compsn. for flexible substrates - contg. acrylic resin based on four monomers and alkylated melamine-formaldehyde resin
US4082862A (en) * 1975-06-24 1978-04-04 Sutures Inc. Process for the production of rubber articles having improved slip coating
US4680335A (en) * 1985-03-20 1987-07-14 Courtaulds Plc Polymer compositions
US5202368A (en) * 1989-01-31 1993-04-13 Ici Australia Operations Proprietary Limited Silicone coating compositions
WO1991005657A1 (en) * 1989-10-18 1991-05-02 Bioresearch, Inc. Articles having improved slip coatings
EP0544569A1 (de) * 1991-11-27 1993-06-02 Rhone-Poulenc Chimie Wässrige Polymerdispersionen aus Styrol/carboxylierten Acrylat-Polymeren und ihre Verwendung als Bindemittel in Klebstoff- und Lackzusammensetzungen
JPH05310857A (ja) * 1992-05-05 1993-11-22 Showa Highpolymer Co Ltd 水性撥水加工用コーティング剤
WO1995029196A1 (en) * 1994-04-20 1995-11-02 Asahi Kasei Kogyo Kabushiki Kaisha Water-base silicone-modified acrylate polymer emulsion
EP0757059A1 (de) * 1994-04-20 1997-02-05 Asahi Kasei Kogyo Kabushiki Kaisha Silikon modifizierte acrylatpolymeremulsion auf wasserbasis
WO1996025279A1 (en) * 1995-02-14 1996-08-22 Allegiance Corporation A multiple dip process for making a powder-free article
US5661208A (en) * 1995-08-11 1997-08-26 Dow Corning Corporation Rubber and vinyl protectant

Non-Patent Citations (1)

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Title
See also references of WO9625278A1 *

Also Published As

Publication number Publication date
MX9706202A (es) 1997-10-31
CN1078123C (zh) 2002-01-23
AU4977596A (en) 1996-09-04
EP0809565A1 (de) 1997-12-03
ID23598A (id) 1996-08-22
CA2212861A1 (en) 1996-08-22
JPH11507085A (ja) 1999-06-22
AU710920B2 (en) 1999-09-30
CN1179745A (zh) 1998-04-22
IL117123A (en) 2002-04-21
WO1996025278A1 (en) 1996-08-22
IL117123A0 (en) 1996-06-18

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