EP1599521A1 - Articles comprenant des dispersions aqueuses de polyurethanne - Google Patents

Articles comprenant des dispersions aqueuses de polyurethanne

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Publication number
EP1599521A1
EP1599521A1 EP04712375A EP04712375A EP1599521A1 EP 1599521 A1 EP1599521 A1 EP 1599521A1 EP 04712375 A EP04712375 A EP 04712375A EP 04712375 A EP04712375 A EP 04712375A EP 1599521 A1 EP1599521 A1 EP 1599521A1
Authority
EP
European Patent Office
Prior art keywords
article
dispersion
mold
aqueous
gloves
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Withdrawn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
EP04712375A
Other languages
German (de)
English (en)
Inventor
Young H. Kim
Jiazhong Chen
Michael Oneill
Portia D. Yarborough
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.)
Invista Technologies Sarl
Original Assignee
Invista Technologies SARL USA
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Filing date
Publication date
Application filed by Invista Technologies SARL USA filed Critical Invista Technologies SARL USA
Publication of EP1599521A1 publication Critical patent/EP1599521A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
    • A61F6/02—Contraceptive devices; Pessaries; Applicators therefor for use by males
    • A61F6/04—Condoms, sheaths or the like, e.g. combined with devices protecting against contagion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • Polyurethane particles dispersed in water can be used to make articles of commerce with reduced chance of chemical and biological allergic reaction to skin, and which exhibit improved puncture and tear resistance when compared to gloves made with other materials.
  • urethane polymers in current use for the manufacture of spandex are made by reacting hydroxy-terminated polyethers or polyesters with a diisocyanate at a molar ratio of about 1 :1.4 to 1 :2.5, followed by reaction of the resulting isocyanate-terminated prepolymer with one or more diamines to produce a high molecular weight urethane polymer. Small amounts of monofunctional amines may also be included to control polymer molecular weight.
  • Mechanical properties may be affected by changing the particular polyester or polyether glycol, diisocyanate, diamine(s), and monoamine used; they can be further modified by changing the molecular weight of the glycol and by changing the glycol- diisocyanate molar ratio.
  • the long-chain urethane polymer molecules in spandex are substantially linear block copolymers comprising relatively long blocks in which molecular interactions are weak, interconnected by shorter blocks in which interactions are strong.
  • the weakly interacting blocks commonly referred to as soft segments, are from the polyether or polyester glycol component whereas the blocks having strong interactions result from diisocyanate and chain extender reactions and are referred to as hard segments.
  • the chain extension reaction is usually a coupling reaction between the isocyanate and difunctional amines, resulting in a urea linkage.
  • the resulting polymer of the combined hard- and soft- segments are known as polyureaurethane.
  • polyisocyanate polymers can be used to prepare aqueous polyurethane dispersions.
  • Polyurethane dispersions are generally prepared by chain extending the reaction product of an organic diisocyanate or polyisocyanate and an organic compound having two or more active hydrogen atoms such as polyalkylene ether glycols, poly(alkylene ether) glycols, alkyd resins, polyesters and polyester amides, often using a small amount of an organic solvent.
  • the diisocyanate is used in stoichiometric excess so that the reaction product, also referred to as a polyurethane/urea prepolymer, is isocyanate terminated. Examples of polyurethane prepolymer preparations are described in U.S. Patents Nos. 3,178,310, 3,919,173, 4,442,259, 4,444,976, and 4,742,095, among others.
  • Polyurethane dispersions are reported as being useful for preparing such diverse materials as coatings and bonds in US Pat. No. 4,292,226; flexible solvent barriers in US Pat. No. 4,431,763; adhesives in US Pat. No. 4,433,095; and films in US Pat. No. 4,501 ,852.
  • Films, or rather the process of dipping to make a film can be a part of the processes for making many articles. Examples of film applications include gloves, organ bags, condoms, ostomy bags, and the like. While it is known that such applications can be made with polyurethane dispersions, conventional polyurethane dispersions have sometimes been found to have insufficient physical or handling properties to make them a preferred material for such applications. Also, the use of certain relatively high-boiling solvents, such as N-methyl-2-pyrrolidone, can have adverse effects for some applications.
  • Polyurethanes are the reaction product of a polyalcohol and a polyisocyanate.
  • the polyisocyanates used to prepare aqueous polyurethane dispersions have been aliphatic isocyanates such as those disclosed in US Pat. No. 5,494,960.
  • aromatic polyisocyanates such as toluene diisocyanate (TDI) and methylene diphenyldiisocyanate (MDI) as well as polymethylene polyphenylisocyanate (PMDI) are also known to be useful
  • TDI toluene diisocyanate
  • MDI methylene diphenyldiisocyanate
  • PMDI polymethylene polyphenylisocyanate
  • Natural rubber latex films prepared from natural rubber latex are common, but are considered to have properties which are desirable from the perspective of comfort and utility.
  • natural rubber latex also includes proteins and other materials, such as sulfur containing curing agents, which can be irritating to the skin, and which may cause severe allergic reactions in some people.
  • PCT International Application No. WO 00/61651 published October 19, 2000, discloses polyurethane films and dispersions for their preparation.
  • the dispersion is prepared from a polyurethane prepolymer formulation including a diisocyanate and an active hydrogen containing material.
  • the dispersion is formed in a two or more step process wherein, in a first step, the prepolymer is formed and, in a subsequent step, an aqueous dispersion of the prepolymer is formed, in the presence of an anionic surfactant, both steps occurring in the substantial absence of an organic solvent.
  • Elastic films with good moisture management can provide protection from the environment, such as germs and chemicals. Particularly with the increased potential threat from chemical and biological agents, the need of such materials is ever increasing. Recent incidents has shown need for a comfortable gloves, which can be worn by law enforcement and postal workers for a long period of time. Latex gloves usually have low puncture resistance, and moreover may pose additional health risks, including fatal allergic reactions by certain individuals. Nitrile gloves have good puncture resistance, but high modulus, so they can cause fatigue with long term use.
  • Polyurethane elastomers may offer an alternative material choice, but some of polyurethane gloves are found to get weak when it is exposed to water or rubbing alcohol. This would hinder the long term use of such gloves.
  • the present invention discloses articles of commerce comprising aqueous polyureaurethane dispersions. These articles have tensile strengths greater than 2030 psi, puncture strengths of greater than 200 lbs/in, and tear strength per thickness of greater than 20 N/mm. They also show improved solvent resistance.
  • a process for producing these articles comprising the steps of: a) dipping a mold into a coagulant solution and drying at an elevated temperature; b) dipping the coagulant solution-coated mold into an aqueous polyureaurethane dispersion and drying; c) subjecting the coated mold to a salt leaching bath; and d) drying the coated mold at elevated temperature before stripping the article off of said mold.
  • This invention discloses the use of stable aqueous polyureaurethane dispersions, using THF homo and/or copolymer as a glycol and an aromatic diisocyanate, but does not require the use of chain extending agents, curing agents or crosslinking agents.
  • a stable colloidal particle of elastomeric polyurethane is generated, which has a wide utility.
  • the process is robust and relatively uncomplicated, in that it does not require a series of separate steps as disclosed in previous work (see for example WO 00/61651).
  • aliphatic isocyanate is preferred for the generation of aqueous colloid of polyurethane. (See generally B. K. Kim, Colloid.
  • aliphatic isocyanates are reacted with various glycols to form oligomeric prepolymers, and then are dispersed into water, containing an equivalent amount of diamine.
  • the amount of diamine is added by equivalence to percent NCO as determined by n-butylamine titration and back calculation.
  • the aliphatic isocyanates have relatively high stability in water so that the diamine reacts with the isocyanate to chain extend the prepolymer through urea linkages.
  • any unreacted amines which remain in the material when made by other processes, can cause skin irritation or sensitivity in certain applications. It has been found that the use of an aromatic diisocyanate under the right reaction temperature and dispersion conditions would be suitable to make the dispersions of this invention. Examples of aromatic diisocyanates are MDI, TDI, PMDI and the like.
  • the amount of NCO % in the prepolymer determines the physical properties of final films produced from the dispersion. The preferred range of NCO % is 2 to 4 %.
  • Another critical element enabling the stability and simplicity of the process is the careful manipulation of polarity of the soft segment.
  • One soft segment which provides a good dispersion, in combination with the conditions for the aqueous dispersion and the right hard segments, is low molecular weight PTMEG with selected acid-functional-group-containing- diols.
  • Another applicable THF copolymer soft segment containing an adequate amount (generally 25 to 60 percent by weight) of ethylene glycol as a comonomer. Methods of preparing such copolymers are disclosed in U.S. Pat. Nos. 4,127,513, 4,139,567, 4,153,186, 4,228,272, 4,235,751; German Pat. Application Nos.
  • hydrophilic soft segments are made by reacting polyurethane prepolymers with an ethylene glycol copolymer of THF with ethylene glycol content higher than 20%, or polyurethane prepolymers with PTMEG with a small amount of sterically-hindered acid containing diols.
  • the preferred range of EO content in the copolymer is 25% to 60% by weight.
  • the preferred hindered acid diol is DMPA.
  • the preferred DMPA range is 3-5 % by weight.
  • the preferred molecular weight of the poly(EO-co-THF) is 1000-3500, and the most preferred molecular weight is 2000.
  • the preferred molecular weight of PTMEG is 700-1500, and the most preferred molecular weight is 1000.
  • the dispersions of the current invention are made by mixing an isocyanate and glycol for several hours under nitrogen at temperatures about 90°C (80°C to 100°C) to form a prepolymer.
  • the shear rate and force to which the dispersion mixture is subjected is important, and is described in Figure 1. If too much shear force is applied, the dispersion can become unstable and break apart. Generally, the preferred range of shear force is between 500 and 1700 Newtons.
  • the mixing time is generally between 2 and 5 minutes. Hindered acid diols (e.g., DMPA and others listed in Table 1 of B. K. Kim, Colloid. Polym. Sci., 274:599-611 (1996) can be added at this step as well.
  • ionic content is by adding hindered acid diol salts (e.g., sodium dimethylolproprionate), adding sulfonates (e.g., 2- sodium 1 ,4 butanediol), or by the addition of cationic centers like the addition of tertiary amines with one alkyl and two alkylol groups.
  • hindered acid diol salts e.g., sodium dimethylolproprionate
  • sulfonates e.g., 2- sodium 1 ,4 butanediol
  • cationic centers like the addition of tertiary amines with one alkyl and two alkylol groups.
  • solvents generally water miscible organic solvents such as acetone and methyl ethyl ketone (MEK)
  • MEK methyl ethyl ketone
  • This solution is pumped into a chilled (i.e., 0 to 10°C) aqueous solution containing surfactant, which can be anionic, cationic or nonionic.
  • surfactant is sodium dodecylbenzenesulfonate or Triton X 100 (Dow Chemical Co., Midland, Ml).
  • the preferred amount of surfactant is 0.1 to 2 % by weight, with the most preferred amount being 0.5 to 1 % by weight.
  • a relatively mild, inorganic base e.g., NaHCO 3 , Na(CO 3 )2, NaAc (where Ac represents acetate), NaH 2 PO 4 and the like
  • inorganic bases are relatively low in odor, and also tend not to be skin irritants.
  • triethyl amine can be used as a base. In this case, using less than one equivalent of amine to the acid, to minimize any potential odor, is recommended.
  • the dispersing water generally contains less than one equivalent of base to neutralize the acid in the DMPA, wherein the pH of the 1 mole aqueous solution does not exceed 10.
  • the dispersion temperature is important for the small particle formation.
  • the preferred dispersion temperature is 0 to 10°C.
  • the solid content of the dispersion is 10-60%, and typically 10-30%.
  • the solids content of the resulting dispersion is generally about 10-30 weight percent, determined by drying the sample in an oven at 100°C for 2 hours and comparing the weights before and after drying.
  • the present invention also uses a urethane polymer comprising a polyester polyol, DMPA and a diisocyanate that is free of, substantially free of, or contains less than 2 percent urea units described by -R-N(R 2 )- C(O)-N(R 2 )-R 1 , wherein R is an aromatic radical, R 1 is an aliphatic radical and R 2 is H or amide groups which can be designated as C(O)-N(R 2 )-R-.
  • This invention relates to these articles which are made from aqueous dispersions as described in co-pending and co-owned patent application number 10/700,859, filed on November 4, 2003, and application number 10/701,317, filed on November 4, 2003, hereby incorporated by reference in their entirety.
  • these materials When used as films and gloves, these materials show improved resistance to solvents, including isopropyl alcohol and DMAc. There is also reduced off-gassing of the film materials, which makes these films and gloves generally acceptable for clean room use. Not only do these films and gloves demonstrate improved chemical and solvent resistance, they also show improved puncture and tear resistance as shown in the examples below. They generally have a modulus of 100% elongation (i.e., between about 200 and 500 psi), allowing the film or glove to be stretched easily. It also shows low set, allowing it to return to its original shape after stretching. The preferred thickness of the gloves is between 3 and 6 mil, but other thicknesses can be used.
  • the dispersions were generally prepared as described in co- pending and co-owned applications application number 10/700,859, filed on November 4, 2003, and application number 10/701 ,317, filed on November 4, 2003, hereby incorporated by reference in their entirety.
  • the glycols were dried at 90 °C under vacuum for 12 h before use. MDI was purified by heating to 50 °C . DMPA, MEK, TEA and SDBS were purchased and were used without further purification.
  • the mixers used to make the dispersions are IKA ® mixer, model T25 BASIC SI, IKA ® Works, Inc and Ross mixer/emulsifier, model HSM-100LC, Charles Ross and Son Company.
  • the IKA® mixer was operated at 11 ,000 rpm, and the Ross mixer was operated between 7,000 and 8,000 rpm.
  • Prepolymer was prepared by mixing MDI, glycol (and DMPA if necessary) at 90 °C for 3-5 h under nitrogen. The amount of excess NCO remained after the coupling reaction was determined by titration. When a solvent was used to dilute the prepolymer, a solvent was added typically to make a 75% weight solution after the reaction product was cooled to room temperature. The prepolymer was placed into a tube and was slowly added into chilled aqueous solution containing surfactant and occasionally base via pneumatic air pump. Solids content of the dispersion is about 10-30 %.
  • a mold is dipped into a coagulant solution.
  • This coagulant solution is typically 10-20% Ca(NO 3 ) 2 and 0-10% CaCO 3 .
  • the mold is then dried at 100°C for 5 minutes.
  • This mold is then dipped into an aqueous polyurethane dispersion at 10-50°C, and then cooled at 10- 40°C.
  • a salt leaching then takes place by dipping the coated mold into water at 20-70°C, and is then subsequently dried for 30 minutes at between 90 and 150°C.
  • the glove is then stripped off of the mold.
  • Comparative Example A A mixture was made as described in Example 3 above, except that no SDBS surfactant was added, and 1.7 g NaHCO 3 was used as a base. The ratio of NaHCO 3 to DMPA is 1:1. No dispersion resulted.
  • Comparative Example B 78 g (0.624 mole) of MDI was mixed with 360 g
  • Comparative Example C The experiment as described in Comparative Example B above was performed, except that a 30%EO/THF material (from Sanyo) was used. No dispersion was made when 2% surfactant/TEA was used, and a large amount of precipitation was noted.
  • Comparative Example D The procedure as described in Example 3 above was followed, except that a 1.25% surfactant/NaHCO3 solution was used. Precipitation was observed. A 10.1% solids content dispersion was obtained after the precipitate was filtered off. The film was cast after water was evaporated. The film showed insufficient elasticity.
  • the puncture strength of gloves made from the dispersions by the method described above was measured according to ASTM Method F1342.
  • the elongation and thickness of the materials were measured.
  • the puncture load was calculated as lbs/inch of thickness. The results are found in Table 1 below.
  • the tear strength of the gloves made by this invention were tested using ASTM method D-624-98. This test requires cutting of films with a die, then putting the samples in an Instron® unit so they tear. The load versus extension is recorded. Dies B and C were used. Specimens for Die B were nicked with a razor to ensure the location of the initial tear. Die C has a sharp 90 degree corner as the location for tearing and was not nicked. The results of the tests are found in Table 2 below, and show the tear strength per unit thickness (N/mm). Table 2

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Vascular Medicine (AREA)
  • Biomedical Technology (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Reproductive Health (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Gloves (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

Des particules de polyuréthanne dispersées dans l'eau peuvent être utilisées pour fabriquer des articles de vente qui présentent un risque réduit de réaction allergique chimique et biologique cutanée, ainsi qu'une résistance à la perforation et à la déchirure améliorée par rapport aux gants formés d'autres matières.
EP04712375A 2003-02-20 2004-02-18 Articles comprenant des dispersions aqueuses de polyurethanne Withdrawn EP1599521A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US44897103P 2003-02-20 2003-02-20
US448971P 2003-02-20
PCT/US2004/004857 WO2004074341A1 (fr) 2003-02-20 2004-02-18 Articles comprenant des dispersions aqueuses de polyurethanne

Publications (1)

Publication Number Publication Date
EP1599521A1 true EP1599521A1 (fr) 2005-11-30

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EP (1) EP1599521A1 (fr)
JP (1) JP4918353B2 (fr)
KR (2) KR101137663B1 (fr)
CN (1) CN1774459B (fr)
TW (1) TWI287552B (fr)
WO (1) WO2004074341A1 (fr)

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DE102004060139A1 (de) * 2004-12-13 2006-06-29 Bayer Materialscience Ag Festkörperreiche Polyurethanpolyharnstoff-Dispersionen
US8765901B2 (en) 2005-05-09 2014-07-01 Invista North America S.ár.l. Spandex compositions for high speed spinning
CN101313002B (zh) 2005-11-22 2012-12-26 因维斯塔技术有限公司 获自与聚合二醇共混的聚(四亚甲基-共聚-亚乙基醚)二醇的弹力纤维
WO2007061446A1 (fr) 2005-11-22 2007-05-31 Invista Technologies S.A.R.L. Elasthanne issu de poly(tetramethylene-co-ethylene ether) glycols de poids moleculaire eleve
MY161156A (en) * 2010-11-18 2017-04-14 Lubrizol Advanced Mat Inc Polymer for surgeons gloves
WO2013035461A1 (fr) * 2011-09-08 2013-03-14 Dic株式会社 Film de polyuréthane et article traité par le film obtenu à l'aide de celui-ci
US10849377B2 (en) 2015-10-30 2020-12-01 Dic Corporation Gloves

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WO2004041893A1 (fr) * 2002-11-04 2004-05-21 Invista Technologies S.À.R.L. Dispersions aqueuses de poly(uree/urethane)

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TWI287552B (en) 2007-10-01
KR101137663B1 (ko) 2012-04-20
TW200516098A (en) 2005-05-16
JP4918353B2 (ja) 2012-04-18
CN1774459B (zh) 2010-05-26
KR20050102128A (ko) 2005-10-25
JP2006520412A (ja) 2006-09-07
KR20110051273A (ko) 2011-05-17
CN1774459A (zh) 2006-05-17
WO2004074341A1 (fr) 2004-09-02

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