WO1997019121A1 - Improved water-based polyurethanes for footwear - Google Patents

Improved water-based polyurethanes for footwear Download PDF

Info

Publication number
WO1997019121A1
WO1997019121A1 PCT/US1996/009501 US9609501W WO9719121A1 WO 1997019121 A1 WO1997019121 A1 WO 1997019121A1 US 9609501 W US9609501 W US 9609501W WO 9719121 A1 WO9719121 A1 WO 9719121A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
polyurethane
footwear
sulfonated
water
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.)
Ceased
Application number
PCT/US1996/009501
Other languages
French (fr)
Inventor
Youlu Duan
Sonja Stammler
Jillian H. Ierien
Brian L. Marty
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.)
HB Fuller Licensing and Financing Inc
Original Assignee
HB Fuller Licensing and Financing Inc
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 HB Fuller Licensing and Financing Inc filed Critical HB Fuller Licensing and Financing Inc
Priority to AU61016/96A priority Critical patent/AU712956B2/en
Priority to EP96918326A priority patent/EP0847409A1/en
Publication of WO1997019121A1 publication Critical patent/WO1997019121A1/en
Anticipated expiration legal-status Critical
Priority to NZ310252A priority patent/NZ310252A/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • 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
    • 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
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate 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
    • 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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds
    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/838—Chemically modified polymers by compounds containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • 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
    • C08G2250/00—Compositions for preparing crystalline polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31558—Next to animal skin or membrane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31591—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal

Definitions

  • This invention relates to water-based adhesives, coatings and primers.
  • water-based polyurethane compositions having improved characteristics such as adhesion, peel strength and heat resistance. More specifically, it relates to one-component water-based sulfonated polyurethane compositions useful as adhesives, coatings and primers in the manufacture of footwear and to footwear and a method of preparing footwear using such compositions.
  • U.S. Pat. No. 5,334,690 discloses water-based sulfonated polyurethanes which are obtained by reacting ionic polyester polyols, polycarbonate polyols and polyether polyols or mixtures thereof with a polyisocyanate or mixtures of polyisocyanates.
  • the water-based sulfonated polyurethane special feature are the ionic groups present in the polyol segment.
  • German Pat. No. DE 3930352 discloses a process for bonding parts of shoes by applying water-based sulfonated polyurethane adhesives and drying with a microwave heater before bringing the parts together.
  • the water-based sulfonated polyurethane Dispercoll U KA-8464 from Bayer Co ⁇ oration is referenced.
  • the article describes water-based sulfonated polyurethane polymers, and their formulations, yielding good adhesion to substrates often used in the manufacture of footwear like PVC, ABS, polyurethanes, nylon, leather and fabrics.
  • a draw back for these prior art compositions is their failure to pass minimum adhesion standards in footwear applications, set by the Association of European Adhesive Manufacturers (FEICA), as one-component formulations.
  • FEICA European Adhesive Manufacturers
  • two-component adhesive formulations are required.
  • bond strengths when subjected to thermal and mechanical stresses can be improved by the addition of water dispersible polyfunctional crosslinking agents selected from a group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines and carbodiimides.
  • water dispersible polyfunctional crosslinking agents selected from a group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines and carbodiimides.
  • a disadvantage associated with two component formulations is their limited pot life due to coagulation, gelling and viscosity increase.
  • two-component adhesives have to be mixed from separate components directly before use. This can give rise to unsati
  • One-component water-based compositions are easier to handle, safer and generally cost less.
  • the present inventors have now discovered new one-component water-based sulfonated polyurethane adhesives compositions which pass FEICA minimum specifications for sole bonding.
  • the present inventors have also discovered two-component water-based sulfonated polyurethane compositions having improved performance over previously known two-component systems. Summary of the Invention
  • the present invention is directed to new water-based sulfonated polyurethane compositions which are useful as adhesives, coatings and primers in the manufacture of footwear, comprising a dispersion in an aqueous vehicle of a reaction product of: a) at least one polyisocyanate component; b) at least one alkylene diol component; c) at least one sulfonated polyester polyol component wherein the sulfo groups are present in the form of alkali metal salts; and d) at least one dihydroxy carboxylic acid or salt thereof selected from the group consisting of alkali metal salts, organic tertiary amine salts and mixtures thereof.
  • carboxyl groups of the dihydroxy carboxylic acid are not in the form of alkali metal salts and/or organic tertiary amine salts at the time of reaction to form the polyurethane polymer, they are converted thereto by the time the polymer is dispersed in the aqueous vehicle.
  • the polymers of the invention are characterized as having low heat activation temperatures in a range from about 50 'C to about 95 * C and rapidly develop heat resistance greater than about 110 * C, without internal or external crosslinking agents.
  • the unique one-component water-based adhesives pass minimum adhesion standards set by the Association of European Adhesive Manufacturers (FEICA).
  • Further formulations of the invention comprise a mixture of: a) a water-based sulfonated polyurethane as previously described; b) at least one non-polyurethane based water dispersible polymer selected from the group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl-acetate/ethylene copolymers, polychloroprenes, styrene emulsions, styrene/butadiene emulsions, starches, dextrins, caseins, animal pectines and mixtures thereof; c) at least one compounding additive selected from a group consisting of thickening agents, surfactants, coalescing aids and plasticizers and mixtures thereof; and optionally, d) at
  • two-component adhesives may be formulated to pass a particular manufacturer's specification.
  • the present invention also comprises two-component water-based polyurethanes which exceed the performance characteristics of two-component water-based adhesives currently available for use in the manufacture of footwear.
  • the water-based sulfonated polyurethane compositions of the present invention generate useful coatings and primers.
  • coatings in the manufacture of footwear, the polymers are tough but flexible, offering a protective layer which acts as a barrier to water, oil, and as solvent.
  • the polymers are especially useful on difficult to adhere to surfaces such as oily leathers and porous substrates.
  • the present invention further comprises water-based sulfonated polyurethane/acrylic or water-based sulfonated polyurethane/vinyl polymers wherein the polyurethanes disclosed above are synthesized in the presence of ethylenically unsaturated monomers to generate useful water-based blends of polyurethane/acrylic-or-vinyl polymers.
  • Such processes are described in U.S. Pat. No. 5, 173,526 (Air Products and Chemicals, Inc.), U.S. Pat No. 4,644,030 (Witco Co ⁇ oration) and EP-A-No. 95101621.1. These processes reduce the use of volatile organic compounds (VOC) and generate polymer blends with enhanced inte ⁇ enetrating polymer networks which ultimately improve the physical properties of the dried films as adhesives, coatings and primers.
  • VOC volatile organic compounds
  • the water-based sulfonated polyurethane compositions and formulations of the present invention outperform existing waterbased products currently available for use in the manufacture of footwear. These characteristics are attributed to the unique properties of the sulfonated polyurethane polymers.
  • the polyurethane is a water-based sulfonated polyurethane wherein the sulfonate functional group is in the soft segment of the polyurethane.
  • polyurethane is defined as a polymer containing two or more urethane groups and is also intended to cover polyurethane-urea polymers. Examples of such polymers are described in copending application Serial No. 08/304/653, filed September 9, 1994.
  • the diisocyanates which are used in forming the sulfonated polyurethane can be aliphatic or aromatic diisocyanates or their mixtures.
  • Suitable aliphatic diisocyanates are isophorone diisocyanate (IPDI), cyclopentylenediisocyanate, cyclohexylenediisocyanate, methylcyclohexylenediisocyanate, dicyclohexylmethanediisocyanate, hexamethylenediisocyanate (HDI), dicyclohexylmethanediisocyanate (H12MDI), and tetramethylxylyenediisocyanate (TMXDI).
  • IPDI isophorone diisocyanate
  • HDI hexamethylenediisocyanate
  • H12MDI dicyclohexylmethanediisocyanate
  • TMXDI tetramethylxylyenediisocyanate
  • aromatic diisocyanates examples include phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate and diphenylmethanediisocyanate (MDI).
  • the alkylene diol component of the sulfonated polyurethane is a C 2 -C 8 alkylene diol or mixture thereof, most preferably a C 3 -C 6 alkylene diol or mixture thereof.
  • the diols are ethylene glycol, 1,3- propylene glycol, 1,4-butanediol (1 ,4-BD) and 1 ,6-hexanediol.
  • the sulfonated polyester polyols used to form the sulfonated polyurethane may be any polyester polyol which incorporates sulfonate groups via sulfonate functional dicarboxylic acid residues and/or sulfonate functional diol residues.
  • the sulfonate functional groups are in alkali salt form.
  • sulfonate functional dicarboxylic acid residues and/or sulfonate functional diol residues are a minor portion of the diol and diacid moieties of the polyester, preferably 1.0%- 10.0% by weight of the polyester.
  • the non-sulfonated diacids and diols used in forming the sulfonated polyesters may be aromatic or aliphatic.
  • Examples of the non-sulfonated diacids include adipic, azelaic, succinic, suberic and phthalic acids.
  • Examples of the non-sulfonated diols include ethylene glycol, condensates of ethylene glycols, butanediol, butenediol, propanediol, neopentylglycol, hexanediol, 1 ,4-cyclohexane dimethanol, 1 ,2-propylene glycol and 2-methyl-l, 3 propanediol.
  • sulfonate diacids examples include sulfoisophthalic acid, 1,3-dihydroxybutane sulfonic acid and sulfosuccinic acid.
  • sulfonate diols examples include 1 ,4 dihydroxybutane sulfonic acid and succinaldehyde disodium bisulfite.
  • dihydroxy carboxylic acids used to form the sulfonated polyurethane are compounds of the formula:
  • the dihydroxy carboxylic acid is an , ⁇ -dimethylol alkanoic acid represented by the formula: CH 2 OH
  • I I CH 2 OH where R' denotes hydrogen or an alkyl group with up to about 20 carbon atoms.
  • R' denotes hydrogen or an alkyl group with up to about 20 carbon atoms.
  • examples of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimefhylolbutyric acid and 2,2-dimethylolpentanic acid.
  • the preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid (DMPA).
  • the carboxylate groups of the dihydroxy carboxylic acid is neutralized to form alkali or tertiary amine alkali groups in order to stabilize the dispersion of the sulfonated polyurethane.
  • the neutralization may be accomplished before, or during dispersion of the sulfonated polyurethane polymer in water.
  • the preferred water-based sulfonated polyurethane is a high molecular weight, crystalline, polyester based polyurethane polymer formed from mixtures of isophorone diisocyanate and hexamethylene diisocyanate.
  • the water-based sulfonated polyurethane solids are present from about 15 parts to about 95 parts by weight, and preferably from about 50 parts to about 95 parts by weight, based on 100 parts total solids. These polymers contain unique properties important in the development of improved adhesives, coatings and primers for footwear.
  • the water-based sulfonated polyurethane compositions contain ionomers, in the soft and hard segments of the molecule, capable of strong hydrogen bonding and ionic dipole interactions.
  • a su ⁇ rising feature of the invention is that the polymers have low heat activation temperatures in a range from about 50 ' C to about 95 "C and rapidly develop high heat resistant bonds greater than about 110' C, preferably greater than about 120°C, without internal or external crosslinking agents.
  • the adhesives, coatings and primers of the invention may also include other non-polyurethane based water dispersible polymers and copolymers selected from a group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl acetate-ethylene copolymers, polychloroprenes, styrene emulsions, styrene-butadiene emulsions, starches, dextrins, caseins, animal pectins and mixtures thereof.
  • the water-based polymer and copolymer solids comprise from about 5 parts to about 95 parts by weight, and preferably from about 5 parts to about 50 parts by weight based on 100 parts total solids.
  • the adhesives, primers, and coatings of the invention may also include compounding additives.
  • Compounding additives include thickening agents, surfactants, coalescing aids and plasticizers.
  • a preferred associative thickening agent is DSX-1550 from Henkel Co ⁇ oration.
  • a preferred non-ionic surfactant is Pentex 99 from Rhone Poulenc.
  • a particularly preferred coalescing aid is Reentry KNI-2000 which is a te ⁇ ene mixture from Environmental Solvents Co ⁇ oration.
  • Useful plasticizers are selected from the group consisting of alkyl and aryl sulfonamides, benzoates esters, phthalate esters, adipates, citrates and mixtures thereof.
  • a preferred plasticizer is Uniplex 108 from Initex Chemical Co ⁇ oration.
  • compounding additives When compounding additives are present in the formulations, their solids content can vary from about 0.5 parts to about 30 parts by weight, and preferably from about 0.5'parts to about 25 parts by weight, based on 100 parts total solids.
  • the formulations may include water dispersible polyfunctional crosslinking agents selected from the group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines, and carbodiimides. Particularly preferred crosslinking agents are water dispersible polyfunctional isocyanates.
  • the amount of crosslinking agent solids can vary from about 3 parts to about 35 parts by weight, and preferably from about 8 parts to about 20 parts by weight, based on 100 parts total solids.
  • the water-based polymer compositions or formulations of the invention can be accomplished in one-side mode or two-side mode.
  • the adhesive is applied to one of two substrates and dried.
  • the adhesive is heat activated and the substrates are brought together with pressure.
  • the adhesive is applied to both substrates, dried, then heat activated and brought together with pressure. It is possible, in both modes, to dry and heat activate the adhesive in the same step.
  • the adhesives can be used either in the aqueous form or in the form of a cast film and are useful in the construction of uppers made of leather, polyurethane, polyvinyl chloride, and textile materials.
  • the adhesives are also useful in sole bonding operations employing cup-sole, welt and stitch-down constructions and can be used for attaching direct injection molded soles.
  • Example 1 describes the synthesis of a preferred water-based sulfonated polyurethane polymer, useful as an adhesive, coating and primer in the manufacture of footwear.
  • Example 1-C Dispercoll U KA-8464, a commercially available water-based sulfonated polyurethane from Mobay Co ⁇ oration.
  • the formulations of Example 1 and Example 1-C were tested for peel adhesion failure temperatures according to the test method described below: 180 " Peel Adhesion Failure Temperature Procedure:
  • the wet samples were drawn down on untreated, pressed, and polished polyvinyl chloride (PVC) sheets with a #40 Meyer rod and dried twenty four hours at ambient room temperature. A second PVC sheet was placed over the dried films and 2.54 x 15.24 centimeter strips were cut. The individual strips were heat activated, using variable temperatures, on a Sentinel heat sealer at 3.515 kilograms per square centimeter for 30 seconds. After 7 days of aging, at ambient room temperature, the strips were placed in a Tenny * oven using 0.1 kilogram weights and subjected to a 25 ' C increase each hour until bond failure. Bond failure temperatures were recorded up to 126 'C by the Tenny * oven sensing unit, and the results are provided below:
  • Example 1 polymer > 126 " C > 126°C > 126°C > 126°C
  • Example 2 was made to compare the 180' peel strengths, bonding various substrates using Dispercoll U KA-8464 and the polymer described in example 1.
  • the adhesive formulations, test procedures and results are described below.
  • the water-based sulfonated polyurethane viscosities were increased to approximately 3000 mPa.s with the associative thickener DSX-1550 from Henkel Co ⁇ oration.
  • the surfactant Pentex 99 from Rhone Poulenc was also added to improve the formulations' wet out characteristics.
  • the formulations were as described below: Materials Example 2 Comparative Example (grams) 2-C
  • SBR Styrene-Butadiene Rubber
  • Nitrile Rubber NBR roughed with 36 grit sandpaper using a belt sander
  • Thermoplastic Rubber SBS or TPR halogenated with a 2% solution of trichloroisocyanuric acid (TCICA) in ethyl acetate, allowed to air dry for 1 hour before applying adhesive
  • the adhesive formulations were then coated on each of the two pieces to be bonded using Meyer rods to generate a total dried coat weight of approximately 175 g/m 2 .
  • the dry adhesive films were heat activated at 70 * C and pressed at 85 psi for 15 seconds.
  • 180' peel strengths were tested on an Instron * 1123 using a cross-head speed of 100 mm/min.
  • the peel strengths were recorded in N/mm.
  • the FEICA specification for sole bonding adhesives is 5.0 N/mm, with an industry standard coat weight of 175 g/m2. The results of these samples are shown below, with coating weights normalized to the standard coating weight.
  • Example 3 was made to compare the adhesive properties of a two-component water-based sulfonated polyurethane of the present invention with a two-component water-based sulfonated polyurethane currently available for use in the manufacture of footwear.
  • the formulation of Example 2 above was further blended with 5 parts crosslinker per 95 parts of wet sample.
  • the crosslinker employed was Desmodur DA which is a water dispersible polyfunctional isocyanate from Miles Inc.
  • the formulations were tested exactly as described in Example 2 bonding SBR to SBR. At an approximate dried coat weight of 130 g/m2, Example 3 exhibited an average peel strength of 7.00 N/mm while the average peel strength of Example 3-C was 4.75 N/mm.
  • Example 3-C is the same as 2-C, except at a coating weight of 135 g/mm.
  • Example 4 This example describes the synthesis and properties of a preferred water-based sulfonated polyurethane/acrylic polymer.
  • the wet sample was drawn down on an untreated, pressed and polished PVC sheet using a number 40 Meyer rod and dried 24 hours at ambient room temperature. A second PVC sheet was placed over the dried film and 2.54 cm x 15.24 cm strips were cut. The individual strips were heat activated, using variable temperatures, on a Sentinel * heat sealer at 3.515 kilograms per square centimeter for
  • the 180' peel adhesion failure temperature was tested using the procedure as described in example 2. The results are provided below:
  • Example 5 This was made in the same manner as Example 1 except the composition of this example did not contain a chain extender.
  • Example 6 The polymer of Example 5 was used to prepare a formulation as follows:
  • Example 6 The Example 6 formulation was tested in the same manner as described in Example 2 and the results are shown below:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

A water-based sulfonated polyurethane composition and footwear manufactured using the composition as an adhesive, coating and primer. The sulfonated polyurethane is a reaction product of (a) at least one polyisocyanate; (b) at least one alkylene diol; (c) at least one sulfonated polyester polyol wherein the sulfo groups thereof are present as alkali metal salts; and (d) at least one dihydroxy carboxylic acid, or salt thereof. The composition may also be modified to include a dispersed polymer or copolymer of an ethylenically unsaturated monomer. Such modified compositions may be obtained by preparing the sulfonated polyurethane in the presence of an ethylenically unsaturated monomer and subsequently subjecting the mixture to free-radical polymerization conditions.

Description

IMPROVED WATER-BASED POLYURETHANES FOR FOOTWEAR
Background of the Invention
Field of the Invention
This invention relates to water-based adhesives, coatings and primers.
Specifically, it relates to water-based polyurethane compositions having improved characteristics such as adhesion, peel strength and heat resistance. More specifically, it relates to one-component water-based sulfonated polyurethane compositions useful as adhesives, coatings and primers in the manufacture of footwear and to footwear and a method of preparing footwear using such compositions.
Description of the Prior Art
It is generally known that water-based sulfonated polyurethanes are useful in the manufacture of footwear. References describing such include the following:
U.S. Pat. No. 5,334,690 (Hoechst Aktiengesellschaft, Fed.) discloses water-based sulfonated polyurethanes which are obtained by reacting ionic polyester polyols, polycarbonate polyols and polyether polyols or mixtures thereof with a polyisocyanate or mixtures of polyisocyanates. The water-based sulfonated polyurethane special feature are the ionic groups present in the polyol segment.
These polymers are described as being especially useful in the production of adhesive bonds for the shoe industry.
German Pat. No. DE 3930352 (REIA GMBH) discloses a process for bonding parts of shoes by applying water-based sulfonated polyurethane adhesives and drying with a microwave heater before bringing the parts together. The water-based sulfonated polyurethane Dispercoll U KA-8464 from Bayer Coφoration is referenced.
"Waterbased high performance adhesive materials", Warrach., Presented at Proceedings of the ASC Division of Polymeric Materials Conference, Miami Beach,
FL. , September 11-18, 1989. The article describes water-based sulfonated polyurethane polymers, and their formulations, yielding good adhesion to substrates often used in the manufacture of footwear like PVC, ABS, polyurethanes, nylon, leather and fabrics.
A draw back for these prior art compositions is their failure to pass minimum adhesion standards in footwear applications, set by the Association of European Adhesive Manufacturers (FEICA), as one-component formulations. To pass minimum adhesion standards, two-component adhesive formulations are required. For example, bond strengths when subjected to thermal and mechanical stresses can be improved by the addition of water dispersible polyfunctional crosslinking agents selected from a group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines and carbodiimides. However, a disadvantage associated with two component formulations is their limited pot life due to coagulation, gelling and viscosity increase. Furthermore, two-component adhesives have to be mixed from separate components directly before use. This can give rise to unsatisfactory adhesive bonds or a shortened pot life through inexact metering of the components making the system less user friendly. Also, exposure to latent crosslinking agents can pose a health risk through skin contact or inhalation.
There remains a need for improved one-component water-based adhesives, coatings and primers. One-component water-based compositions are easier to handle, safer and generally cost less. The present inventors have now discovered new one-component water-based sulfonated polyurethane adhesives compositions which pass FEICA minimum specifications for sole bonding. The present inventors have also discovered two-component water-based sulfonated polyurethane compositions having improved performance over previously known two-component systems. Summary of the Invention
The present invention is directed to new water-based sulfonated polyurethane compositions which are useful as adhesives, coatings and primers in the manufacture of footwear, comprising a dispersion in an aqueous vehicle of a reaction product of: a) at least one polyisocyanate component; b) at least one alkylene diol component; c) at least one sulfonated polyester polyol component wherein the sulfo groups are present in the form of alkali metal salts; and d) at least one dihydroxy carboxylic acid or salt thereof selected from the group consisting of alkali metal salts, organic tertiary amine salts and mixtures thereof. If the carboxyl groups of the dihydroxy carboxylic acid are not in the form of alkali metal salts and/or organic tertiary amine salts at the time of reaction to form the polyurethane polymer, they are converted thereto by the time the polymer is dispersed in the aqueous vehicle.
Suφrisingly, the polymers of the invention are characterized as having low heat activation temperatures in a range from about 50 'C to about 95 *C and rapidly develop heat resistance greater than about 110* C, without internal or external crosslinking agents. The unique one-component water-based adhesives pass minimum adhesion standards set by the Association of European Adhesive Manufacturers (FEICA).
In order to meet requirements in footwear applications, such as wet out, viscosity, green strength, peel strength, water resistance, heat resistance and cost, it maybe desirable to compound the water-based sulfonated polyurethanes. Further formulations of the invention comprise a mixture of: a) a water-based sulfonated polyurethane as previously described; b) at least one non-polyurethane based water dispersible polymer selected from the group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl-acetate/ethylene copolymers, polychloroprenes, styrene emulsions, styrene/butadiene emulsions, starches, dextrins, caseins, animal pectines and mixtures thereof; c) at least one compounding additive selected from a group consisting of thickening agents, surfactants, coalescing aids and plasticizers and mixtures thereof; and optionally, d) at least one water dispersible polyfunctional crosslinking agent selected from the group consisting of isocyanates, aziridines, melamine resins, epoxies and carbodiimides and mixtures thereof. Because adhesion properties can vary with coating weights and substrates, two-component adhesives may be formulated to pass a particular manufacturer's specification. The present invention also comprises two-component water-based polyurethanes which exceed the performance characteristics of two-component water-based adhesives currently available for use in the manufacture of footwear.
The water-based sulfonated polyurethane compositions of the present invention generate useful coatings and primers. As coatings, in the manufacture of footwear, the polymers are tough but flexible, offering a protective layer which acts as a barrier to water, oil, and as solvent. As a primer, the polymers are especially useful on difficult to adhere to surfaces such as oily leathers and porous substrates.
The present invention further comprises water-based sulfonated polyurethane/acrylic or water-based sulfonated polyurethane/vinyl polymers wherein the polyurethanes disclosed above are synthesized in the presence of ethylenically unsaturated monomers to generate useful water-based blends of polyurethane/acrylic-or-vinyl polymers. Such processes are described in U.S. Pat. No. 5, 173,526 (Air Products and Chemicals, Inc.), U.S. Pat No. 4,644,030 (Witco Coφoration) and EP-A-No. 95101621.1. These processes reduce the use of volatile organic compounds (VOC) and generate polymer blends with enhanced inteφenetrating polymer networks which ultimately improve the physical properties of the dried films as adhesives, coatings and primers.
The water-based sulfonated polyurethane compositions and formulations of the present invention outperform existing waterbased products currently available for use in the manufacture of footwear. These characteristics are attributed to the unique properties of the sulfonated polyurethane polymers.
Detailed Description of the Invention In the instant invention, the polyurethane is a water-based sulfonated polyurethane wherein the sulfonate functional group is in the soft segment of the polyurethane. The term "polyurethane" is defined as a polymer containing two or more urethane groups and is also intended to cover polyurethane-urea polymers. Examples of such polymers are described in copending application Serial No. 08/304/653, filed September 9, 1994.
The diisocyanates which are used in forming the sulfonated polyurethane can be aliphatic or aromatic diisocyanates or their mixtures.
Examples of suitable aliphatic diisocyanates are isophorone diisocyanate (IPDI), cyclopentylenediisocyanate, cyclohexylenediisocyanate, methylcyclohexylenediisocyanate, dicyclohexylmethanediisocyanate, hexamethylenediisocyanate (HDI), dicyclohexylmethanediisocyanate (H12MDI), and tetramethylxylyenediisocyanate (TMXDI). Examples of suitable aromatic diisocyanates are phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate and diphenylmethanediisocyanate (MDI).
Preferably, the alkylene diol component of the sulfonated polyurethane is a C2-C8 alkylene diol or mixture thereof, most preferably a C3-C6 alkylene diol or mixture thereof. Examples of the diols are ethylene glycol, 1,3- propylene glycol, 1,4-butanediol (1 ,4-BD) and 1 ,6-hexanediol. The sulfonated polyester polyols used to form the sulfonated polyurethane may be any polyester polyol which incorporates sulfonate groups via sulfonate functional dicarboxylic acid residues and/or sulfonate functional diol residues. The sulfonate functional groups are in alkali salt form. Typically such sulfonate functional dicarboxylic acid residues and/or sulfonate functional diol residues are a minor portion of the diol and diacid moieties of the polyester, preferably 1.0%- 10.0% by weight of the polyester. The non-sulfonated diacids and diols used in forming the sulfonated polyesters may be aromatic or aliphatic. Examples of the non-sulfonated diacids include adipic, azelaic, succinic, suberic and phthalic acids. Examples of the non-sulfonated diols include ethylene glycol, condensates of ethylene glycols, butanediol, butenediol, propanediol, neopentylglycol, hexanediol, 1 ,4-cyclohexane dimethanol, 1 ,2-propylene glycol and 2-methyl-l, 3 propanediol. Examples of the sulfonate diacids include sulfoisophthalic acid, 1,3-dihydroxybutane sulfonic acid and sulfosuccinic acid. Examples of the sulfonate diols include 1 ,4 dihydroxybutane sulfonic acid and succinaldehyde disodium bisulfite.
The dihydroxy carboxylic acids used to form the sulfonated polyurethane are compounds of the formula:
(HO) 2RCOOH wherein R represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms. Preferably, the dihydroxy carboxylic acid is an ,α-dimethylol alkanoic acid represented by the formula: CH2OH
I
R^ C- COOH
I I CH2OH where R' denotes hydrogen or an alkyl group with up to about 20 carbon atoms. Examples of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimefhylolbutyric acid and 2,2-dimethylolpentanic acid. The preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid (DMPA).
The carboxylate groups of the dihydroxy carboxylic acid is neutralized to form alkali or tertiary amine alkali groups in order to stabilize the dispersion of the sulfonated polyurethane. The neutralization may be accomplished before, or during dispersion of the sulfonated polyurethane polymer in water.
The preferred water-based sulfonated polyurethane is a high molecular weight, crystalline, polyester based polyurethane polymer formed from mixtures of isophorone diisocyanate and hexamethylene diisocyanate. The water-based sulfonated polyurethane solids are present from about 15 parts to about 95 parts by weight, and preferably from about 50 parts to about 95 parts by weight, based on 100 parts total solids. These polymers contain unique properties important in the development of improved adhesives, coatings and primers for footwear. The water-based sulfonated polyurethane compositions contain ionomers, in the soft and hard segments of the molecule, capable of strong hydrogen bonding and ionic dipole interactions. It is surmised that the strong intermolecular forces and high degree of crystallization, inherent in these polymers, generate enhanced thermal and solvent resistance properties as well as good adhesion through mechanical interlocking. A suφrising feature of the invention is that the polymers have low heat activation temperatures in a range from about 50 ' C to about 95 "C and rapidly develop high heat resistant bonds greater than about 110' C, preferably greater than about 120°C, without internal or external crosslinking agents.
The adhesives, coatings and primers of the invention may also include other non-polyurethane based water dispersible polymers and copolymers selected from a group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl acetate-ethylene copolymers, polychloroprenes, styrene emulsions, styrene-butadiene emulsions, starches, dextrins, caseins, animal pectins and mixtures thereof. When present in the formulations, the water-based polymer and copolymer solids comprise from about 5 parts to about 95 parts by weight, and preferably from about 5 parts to about 50 parts by weight based on 100 parts total solids.
The adhesives, primers, and coatings of the invention may also include compounding additives. Compounding additives include thickening agents, surfactants, coalescing aids and plasticizers. A preferred associative thickening agent is DSX-1550 from Henkel Coφoration. A preferred non-ionic surfactant is Pentex 99 from Rhone Poulenc. A particularly preferred coalescing aid is Reentry KNI-2000 which is a teφene mixture from Environmental Solvents Coφoration. Useful plasticizers are selected from the group consisting of alkyl and aryl sulfonamides, benzoates esters, phthalate esters, adipates, citrates and mixtures thereof. A preferred plasticizer is Uniplex 108 from Initex Chemical Coφoration. When compounding additives are present in the formulations, their solids content can vary from about 0.5 parts to about 30 parts by weight, and preferably from about 0.5'parts to about 25 parts by weight, based on 100 parts total solids.
As two-component adhesives, primers, and coatings, the formulations may include water dispersible polyfunctional crosslinking agents selected from the group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines, and carbodiimides. Particularly preferred crosslinking agents are water dispersible polyfunctional isocyanates. When present in the formulations, the amount of crosslinking agent solids can vary from about 3 parts to about 35 parts by weight, and preferably from about 8 parts to about 20 parts by weight, based on 100 parts total solids.
As an adhesive, the water-based polymer compositions or formulations of the invention can be accomplished in one-side mode or two-side mode. In the one-side mode, the adhesive is applied to one of two substrates and dried. The adhesive is heat activated and the substrates are brought together with pressure. In the two-side mode, the adhesive is applied to both substrates, dried, then heat activated and brought together with pressure. It is possible, in both modes, to dry and heat activate the adhesive in the same step.
The adhesives can be used either in the aqueous form or in the form of a cast film and are useful in the construction of uppers made of leather, polyurethane, polyvinyl chloride, and textile materials. The adhesives are also useful in sole bonding operations employing cup-sole, welt and stitch-down constructions and can be used for attaching direct injection molded soles.
To successfully prepare the adhesive, primer, and coating formulations a sequential mix process is used. The water-based sulfonated polyurethane and water-based sulfonated polyurethane/acrylic-or-vinyl polymers are blended with other non-polyurethane based water dispersible polymers and copolymers. Compounding additives are then blended in with mild agitation. If two-component formulations are required, the water dispersible polyfunctional crosslinking agents must be mixed into the formulations directly before use. The present invention is further illustrated by the following non-limiting examples.
Examples
Example 1 & Comparative Example 1-C
Example 1 describes the synthesis of a preferred water-based sulfonated polyurethane polymer, useful as an adhesive, coating and primer in the manufacture of footwear.
To a reaction flask was charged 21.43 grams (0.021 hydroxyl equivalents) of molten Rucoflex* XS-5483-55 which is a sulfonated polyester polyol from Ruco Polymer Coφoration, 1.00 grams (0.015 hydroxyl equivalents) dimethylolpropionic acid, and 1.127 grams (0.025 hydroxyl equivalents)
1 ,4-butanediol. The mixture was heated to 55 ' C then charged with 3.11 grams
(0.0279 isocyanate equivalents) isophorone diisocyanate, 4.71 grams (0.056 isocyanate equivalents) 1,6-diisocyantohexane, and 7.01 grams (solvent) anhydrous acetone. The mixture was heated at 70 * C for approximately 3 hours then cooled to 55 " C. The isocyanate terminated prepolymer was charged with 0.60 grams (.006 moles) triethylamine then stirred for 10 minutes. The prepolymer was then dispersed in 55.43 grams deionized water and chain extended with a solution containing 0.54 grams (0.02 amine equivalents) ethylenediamine and 5.0 grams deionized water. The aqueous properties are described below: pH = 8.0
Solids = 35% Viscosity = 250 mPa.s Color wet = White The formulation of comparative Example 1-C is Dispercoll U KA-8464, a commercially available water-based sulfonated polyurethane from Mobay Coφoration. The formulations of Example 1 and Example 1-C were tested for peel adhesion failure temperatures according to the test method described below: 180" Peel Adhesion Failure Temperature Procedure:
The wet samples were drawn down on untreated, pressed, and polished polyvinyl chloride (PVC) sheets with a #40 Meyer rod and dried twenty four hours at ambient room temperature. A second PVC sheet was placed over the dried films and 2.54 x 15.24 centimeter strips were cut. The individual strips were heat activated, using variable temperatures, on a Sentinel heat sealer at 3.515 kilograms per square centimeter for 30 seconds. After 7 days of aging, at ambient room temperature, the strips were placed in a Tenny* oven using 0.1 kilogram weights and subjected to a 25 ' C increase each hour until bond failure. Bond failure temperatures were recorded up to 126 'C by the Tenny* oven sensing unit, and the results are provided below:
Test Sample 51.6'C 65.5 " C 79.4'C 93.3 'C
Example 1 polymer > 126"C > 126°C > 126°C > 126°C
Example 1-C 93 'C 104 ' C 105 *C 106'C
Example 2 & Comparative Example 2-C
Example 2 was made to compare the 180' peel strengths, bonding various substrates using Dispercoll U KA-8464 and the polymer described in example 1. The adhesive formulations, test procedures and results are described below. The water-based sulfonated polyurethane viscosities were increased to approximately 3000 mPa.s with the associative thickener DSX-1550 from Henkel Coφoration. The surfactant Pentex 99 from Rhone Poulenc was also added to improve the formulations' wet out characteristics. The formulations were as described below: Materials Example 2 Comparative Example (grams) 2-C
(grams)
Example #1 Polymer 99.18 —
Dispercoll U KA-8464 — 94.40
DSX-1550/water (50/50) 0.56 0.32
Pentex 99 0.26 0.24
Desmodur DA — 5.0
Test procedures were performed in accordance with the Association of European Adhesive Manufacturers (FEICA). Initially, 2.54 centimeter by 15.24 centimeter strips of substrate were surface treated using the following materials and methods:
Substrate Surface Preparation
Leather roughed with 36 grit sandpaper using a belt sander
Styrene-Butadiene Rubber(SBR) roughed with 36 grit sandpaper using a belt sander
Nitrile Rubber (NBR) roughed with 36 grit sandpaper using a belt sander
Thermoplastic Rubber (SBS or TPR) halogenated with a 2% solution of trichloroisocyanuric acid (TCICA) in ethyl acetate, allowed to air dry for 1 hour before applying adhesive
Polyvinylchloride (PVC) wiped with ethyl acetate
The adhesive formulations were then coated on each of the two pieces to be bonded using Meyer rods to generate a total dried coat weight of approximately 175 g/m2. The dry adhesive films were heat activated at 70 *C and pressed at 85 psi for 15 seconds. After 5 days aging at 23 "C and 50% relative humidity, 180' peel strengths were tested on an Instron* 1123 using a cross-head speed of 100 mm/min. The peel strengths were recorded in N/mm. The FEICA specification for sole bonding adhesives is 5.0 N/mm, with an industry standard coat weight of 175 g/m2. The results of these samples are shown below, with coating weights normalized to the standard coating weight. leather/SBR SBR/SBR NBR/NBR PVC/PVC SBS/SBS
Example 2 3.47 3.89 2.40 5.36 7.60
Comparative 2.80 1.63 3.20 1.46 1.27 Example 2-C
Different coating weights, actual, were also made for bonding PVC to PVC. The results of these weight variations, and the peel adhesion differences, are shown below:
Coat Weight 76 - 152 -228 - 304 -380 (g/m2)
Example 2 3.66 4.87 6.48 8.63 11.49
Example 3 & Comparative Example 3-C Example 3 was made to compare the adhesive properties of a two-component water-based sulfonated polyurethane of the present invention with a two-component water-based sulfonated polyurethane currently available for use in the manufacture of footwear. The formulation of Example 2 above was further blended with 5 parts crosslinker per 95 parts of wet sample. The crosslinker employed was Desmodur DA which is a water dispersible polyfunctional isocyanate from Miles Inc. The formulations were tested exactly as described in Example 2 bonding SBR to SBR. At an approximate dried coat weight of 130 g/m2, Example 3 exhibited an average peel strength of 7.00 N/mm while the average peel strength of Example 3-C was 4.75 N/mm. Example 3-C is the same as 2-C, except at a coating weight of 135 g/mm.
Example 4 This example describes the synthesis and properties of a preferred water-based sulfonated polyurethane/acrylic polymer.
To a reaction flask was charged 213.8 grams (0.21 hydroxyl equivalents) of molten Rucoflex XS-5483-55 which is a sulfonated polyester polyol from Ruco Coφoration, 10.05 grams (0.15 hydroxyl equivalents) dimethylolpropionic acid, 6.75 grams (0.15 hydroxyl equivalents) 1,4-butanediol, 37.97 grams methyl methacrylate and 37.97 grams butyl acrylate. The mixture was heated to 55 *C then charged with 25.9 grams (0.23 isocyanate equivalents) isophorone diisocyanate and 39.2 grams (0.46 isocyanate equivalents)
1 ,6-diisocyantohexane. The mixture was heated at 70"C for approximately 3 hours. The isocyanate terminated sulfonated polyurethane prepolymer/monomer mixture was then charged with 8.0 grams (0.8 moles) triethylamine and stirred for 10 minutes. The prepolymer was dispersed in 554.5 grams deionized water. To the dispersion was charged, over a 10 minute period, a solution containing 0.20 grams ammonium peroxydisulfate and 20 grams deionized water. Free radical emulsion polymerization was completed by heating to 80 "C for approximately 3 hours. The aqueous and dried polymer properties are described below: pH = 7.7
Viscosity = 900 mPa.s Effective diameter = 228 nm Mean diameter = 494 nm
Adhesion testing:
The wet sample was drawn down on an untreated, pressed and polished PVC sheet using a number 40 Meyer rod and dried 24 hours at ambient room temperature. A second PVC sheet was placed over the dried film and 2.54 cm x 15.24 cm strips were cut. The individual strips were heat activated, using variable temperatures, on a Sentinel* heat sealer at 3.515 kilograms per square centimeter for
30 seconds. After 24 and 168 hours aging, at ambient room temperature, the strips were tested on a Intellect* 500 for 180" peel values. The results are provided below:
Aging 51.6'C 65.5 'C 79.4'C 93.3 'C
24 hours 2.1 kg/cm 3.0 Kg/cm 4.4 Kg/cm 5.3 Kg/cm
168 hours 3.2 Kg/cm SF SF SF
SF = Substrate Failure
The 180' peel adhesion failure temperature was tested using the procedure as described in example 2. The results are provided below:
Heat activation 51.6'C 65.5'C 79.4'C 93.3 'C Temperature
Failure Temperature 58.7'C > 126"C > 126'C > 126'C Example 5 This was made in the same manner as Example 1 except the composition of this example did not contain a chain extender.
Example 6 The polymer of Example 5 was used to prepare a formulation as follows:
Example 6
Example 5 polymer 99.45
DSX-1550/water (50/50) 0.05
Surfynol 465 0.05
The Example 6 formulation was tested in the same manner as described in Example 2 and the results are shown below:
Leather/SBR SBR/SBR NBR/NBR PVC/PVC SBS/SBS
Example 6 3.84 7.30 7.43 11.30 11.47
Comparative 2.80 1.63 3.20 1.46 1.27 Example 2-C

Claims

ClaimsWhat is claimed is:
1. An improved water-based sulfonated polyurethane composition particularly useful as an adhesive, coating and primer in the manufacture of footwear, said sulfonated polyurethane being a reaction product of a) at least one polyisocyanate; b) at least one alkylene diol; c) at least one sulfonated polyester polyol wherein the sulfo groups thereof are present as alkali metal salts; and d) at least one dihydroxy carboxylic acid, or salt thereof; the carboxyl groups of said dihydroxy carboxylic acid being present in said dispersion as alkali metal salts, organic tertiary amine salts or mixtures thereof.
2. A composition as in claim 1 wherein said polyisocyanate is an aliphatic polyisocyanate.
3. A composition as in claim 2 wherein said dihydroxy carboxylic acid is dimethylolpropionic acid.
4. A composition as in claim 2 wherein said polydiisocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate and mixtures thereof.
5. A composition as in claim 1 wherein said composition is characterized as having a dried film heat activation temperature in the range of from about 50 'C to about 95 ' C and heat resistant bonds of greater than I IO' C.
6. A composition as in claim 1 further comprising at least one water dispersible polyfunctional crosslinking agent.
7. A composition as in claim 6 wherein said crosslinking agent is selected from the group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines and carbodiimides.
8. A composition as in claim 7 wherein said crosslinking agent is present in the composition in an amount from about 8 to about 20 parts by weight, based on 100 parts total solids.
9. A composition as in claim 8 wherein said water dispersible polyfunctional crosslinking agent is a water dispersible polyfunctional isocyanate.
10. A composition as in claim 9 wherein said composition is characterized as having a dried film heat activation temperature in a range from about 50 *C to about 95 "C and heat resistant bonds greater than about I IO'C.
11. A composition as in claim 1 further comprising at least one dispersible non-polyurethane based polymer and copolymer selected from the group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl-acetate/ethylene copolymers, polychloroprenes, styrene, styrene/butadiene, starches, dextrins, caseins, animal pectins and mixtures thereof.
12. An improved water-based sulfonated polyurethane composition, particularly useful as an adhesive, coating or primer in the manufacture of footwear, the composition comprising an aqueous dispersion of a sulfonated polyurethane polymer formed in the presence of at least one ethylenically unsaturated monomer.
13. A composition as in claim 12 wherein said ethylenically unsaturated monomer is selected from the group consisting of methyl methacrylate, butyl acrylate and mixtures thereof.
14. A composition as in claim 13 wherein said at least one ethylenically unsaturated monomer is free radically polymerized after formation of said sulfonated polyurethane to form a water-based sulfonated polyurethane/acrylic inteφretating network.
15 A composition as in claim 14 wherein said composition is characterized as having a dried film heat activation temperature in a range from about 50 "C to about 95 " C and heat resistant bonds of greater than I IO'C.
16. A composition as in claim 14 further comprising at least one water dispersible polyfunctional crosslinking agent.
17. A composition as in claim 16 wherein said crosslinking agent is selected from the group consisting of isocyanates, aziridines, melamine resins, epoxies, oxazolines and carbodiimides.
18. A composition as in claim 17 wherein said crosslinking agent is present in the composition in an amount from about 8 to about 20 parts by weight, based on 100 parts total solids.
19. A footwear adhesive as in claim 17 wherein said water dispersible polyfunctional crosslinking agent is a water dispersible polyfunctional isocyanate.
20. A composition as in claim 14 further comprising at least one water dispersible non-polyurethane based polymer or copolymer selected from the group consisting of acrylics, vinyl/acrylics, styrene/acrylics, vinyl-acetate/ethylene copolymers, polychloroprenes, styrene, styrene/butadiene, starches, dextrins, casein, animal pectin and mixtures thereof.
21. A method of bonding a pair of substrates comprising applying a composition as in claim 1 to at least one of said substrates, drying said composition and then joining the two substrates with heat and pressure.
22. A bonded assembly prepared by the method of claim 21 wherein at least one of said substrates is a member selected from the group consisting of leather, polyvinyl chloride, polyurethane, cloth, nylon fabric, vulcanized rubbers, ethylene vinyl acetate, polypropylene, polyamide, styrene butadiene copolymers, natural rubber, fiberboard, polyester, polystyrene, wood, nylon and polyethylene.
23. In a method of manufacturing an article of footwear wherein a composition comprising an aqueous dispersion of a polyurethane polymer is utilized as an adhesive, coating or primer on at least one portion of said article of footwear, the improvement wherein the polyurethane polymer is a reaction product of a) at least one polyisocyanate; b) at least one alkylene diol; c) at least one sulfonated polyester polyol wherein the sulfo groups are present as alkali metal salts; and d) at least one dihydroxy carboxylic acid, or salt thereof; the carboxyl groups of said dihydroxy carboxylic acid being present in said dispersion as alkali metal salts, organic tertiary amine salts and mixtures thereof.
24. An article of footwear having an adhesive, coating or primer layer on at least one portion thereof, said layer comprising a polyurethane polymer, said polyurethane polymer being a reaction product of a) at least one polyisocyanate; b) at least one alkylene diol; c) at least one sulfonated polyester polyol wherein the sulfo groups are present as alkali metal salts; and d) at least one dihydroxy carboxylic acid, or a salt thereof selected from the group consisting of alkali metal salts, organic tertiary amine salts and mixtures thereof.
25. An article of footwear as in claim 24 wherein said layer comprises a dried film of an aqueous dispersion comprising said polyurethane polymer and or copolymer of an ethylenically unsaturated compound.
PCT/US1996/009501 1994-09-09 1996-06-07 Improved water-based polyurethanes for footwear Ceased WO1997019121A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU61016/96A AU712956B2 (en) 1994-09-09 1996-06-07 Improved water-based polyurethanes for footwear
EP96918326A EP0847409A1 (en) 1995-11-21 1996-06-07 Improved water-based polyurethanes for footwear
NZ310252A NZ310252A (en) 1995-11-21 1998-06-07 Sulphonated polyurethane water based compositions being a reaction product from a polyisocyanate, alkylene diol, sulfonated polyester polyol and dihydroxy carboxylic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/561,197 US5872182A (en) 1994-09-09 1995-11-21 Water-based polyurethanes for footwear
US08/561,197 1995-11-21

Publications (1)

Publication Number Publication Date
WO1997019121A1 true WO1997019121A1 (en) 1997-05-29

Family

ID=24241037

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/009501 Ceased WO1997019121A1 (en) 1994-09-09 1996-06-07 Improved water-based polyurethanes for footwear

Country Status (7)

Country Link
US (1) US5872182A (en)
EP (1) EP0847409A1 (en)
AR (1) AR004275A1 (en)
CA (1) CA2233083A1 (en)
NZ (1) NZ310252A (en)
TW (1) TW349961B (en)
WO (1) WO1997019121A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717025A (en) * 1996-09-16 1998-02-10 H. B. Fuller Licensing & Financing, Inc. Melamine-formaldehyde resin based adhesive compositions
US6180244B1 (en) 1998-02-17 2001-01-30 3M Innovative Properties Company Waterbased thermoforming adhesives
US6306942B1 (en) 2000-04-05 2001-10-23 3M Innovative Properties Company Low temperature thermally activated water-dispersed adhesives
US6310125B1 (en) 2000-04-05 2001-10-30 3M Innovative Properties Company Water-dispersed adhesive compositions
US6444737B1 (en) 2000-04-05 2002-09-03 3M Innovative Properties Company Water-dispersed polymer stabilizer
US6541550B1 (en) 2000-04-05 2003-04-01 3M Innovative Properties Company Low temperature thermally activated water-dispersed adhesive compositions
EP1382622A1 (en) 2002-07-19 2004-01-21 Dainippon Ink And Chemicals, Inc. Aqueous polyurethane resin dispersion and aqueous adhesive
KR100528122B1 (en) * 1998-12-30 2006-01-27 에스케이케미칼주식회사 Water based polyurethane adhesive composition
WO2012069412A1 (en) * 2010-11-26 2012-05-31 Bayer Materialscience Ag Use of aqueous dispersions as primers
CN108102443A (en) * 2010-11-26 2018-06-01 科思创德国股份有限公司 Use of aqueous dispersions as primers

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19837856A1 (en) * 1998-08-20 2000-02-24 Wacker Chemie Gmbh Protective colloid-stabilized polymer compositions
US6716384B2 (en) 1999-03-23 2004-04-06 Teresa Banks Process for the rotational molding of polyurethane articles
US6740705B2 (en) * 2000-06-17 2004-05-25 Imperial Chemical Industries Plc Process for making poly (urethane-urea)/addition polymer composite particles
GB0014762D0 (en) * 2000-06-17 2000-08-09 Ici Plc A process for making poly(urethane-urea) addition polyner composite particles which can be obtained as aqueous dispersions
KR100635293B1 (en) * 2000-10-25 2006-10-19 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 Aqueous dispersion of polyurethane resins and aqueous adhesives
WO2002036524A1 (en) * 2000-11-01 2002-05-10 Valspar Sourcing, Inc. Abrasion resistant coating for stacks of fiber cement siding
US6984287B2 (en) * 2001-11-02 2006-01-10 The Dow Chemical Company Primer composition for promoting adhesion of a urethane adhesive to a polymeric substrate
US20040153006A1 (en) * 2003-02-03 2004-08-05 Scimed Life Systems, Inc. Intracorporeal devices with ionomeric polymer sleeves
US20070027249A1 (en) * 2003-08-13 2007-02-01 Valspar Sourcing, Inc. Water-based polyurethane-polyethylene compositions
US20070032561A1 (en) * 2005-08-05 2007-02-08 I-Sioun Lin Modified hydrophilic polyurethane memory foam, application and manufacturing method thereof
KR100927870B1 (en) * 2009-03-09 2009-11-23 대륭기업 주식회사 Aqueous adhesive composition for sess-based shock absorbing material
US20110079346A1 (en) * 2009-10-05 2011-04-07 Barbara Strickland Water based bonding compound and method
TW201117740A (en) * 2009-11-20 2011-06-01 Tsung-Ta Wu Seamless waterproof TPU shoes
JP5496287B2 (en) 2011-09-15 2014-05-21 ローム アンド ハース カンパニー Low gloss aqueous coating composition containing poly (ethylene oxide) for use in leather
JP5781037B2 (en) 2011-09-15 2015-09-16 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ Low gloss aqueous coating composition comprising poly (ethylene oxide)
US9398820B2 (en) 2012-06-13 2016-07-26 Noa Brands America, Inc. Manikin stretch joint
KR20210133248A (en) 2019-03-27 2021-11-05 헨켈 아게 운트 코. 카게아아 Two-component water-based lamination adhesives and their use for bonding substrates and foams
CN112724655B (en) * 2020-12-28 2022-07-19 上海汇得科技股份有限公司 Polyurethane resin composition and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0259679A1 (en) * 1986-09-04 1988-03-16 Bayer Ag Adhesive and the use of the adhesive in producing bonds
EP0368172A2 (en) * 1988-11-08 1990-05-16 Toyo Boseki Kabushiki Kaisha A magnetic recording medium
DE3930352A1 (en) * 1989-09-12 1991-03-21 Renia Gmbh Bonding shoe parts, esp. for shoe repair - by applying solvent-free polyurethane dispersion adhesive and drying in microwave oven before bringing parts together
WO1995008583A1 (en) * 1993-09-24 1995-03-30 H.B. Fuller Licensing & Financing, Inc. Aqueous anionic polyurethane dispersions
EP0666275A2 (en) * 1994-02-08 1995-08-09 Air Products And Chemicals, Inc. Organic solvent free urethane/acrylic polymer laminating adhesive for flexible packaging
US5455293A (en) * 1994-06-06 1995-10-03 Wood; Benny R. Water dispersible polyurethane adhesive
WO1996007540A1 (en) * 1994-09-09 1996-03-14 H.B. Fuller Licensing And Financing, Inc. Aqueous polyurethane dispersion adhesive compositions with improved heat resistance

Family Cites Families (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA764009A (en) * 1967-07-25 Keberle Wolfgang Polyurethane plastics
NL126422C (en) * 1960-10-14
DE1495745C3 (en) * 1963-09-19 1978-06-01 Bayer Ag, 5090 Leverkusen Process for the production of aqueous, emulsifier-free polyurethane latices
DE1200318B (en) * 1964-01-16 1965-09-09 Bayer Ag Process for the preparation of N- (omega-aminoalkyl) -aminoalkanesulfonic acids
GB1070759A (en) * 1964-02-13 1967-06-01 Goodyear Tire & Rubber Polyurethanes and method of making
US3358005A (en) * 1964-11-24 1967-12-12 Merck & Co Inc Polyurethanes and polyureas from diisocyanates
FR1499121A (en) * 1964-12-08 1968-01-12
DE1570615C3 (en) * 1965-10-16 1975-05-28 Bayer Ag, 5090 Leverkusen Process for the production of dispersible polyurethanes
BE757936A (en) * 1969-10-23 1971-04-01 Bayer Ag PROCESS FOR PREPARING ANIONIC MODIFIED POLYMERS IN EMULSION
US3870684A (en) * 1970-04-29 1975-03-11 Bayer Ag Preparation of cross-linked particles of polyurethane or polyurea containing ionic groups
DE2035732A1 (en) * 1970-07-18 1972-01-27 Farbenfabriken Bayer AG, 5090 Le verkusen N (omega ammo a / kan) omega ammo a / kan sulfonic acid salts and their use as anionic structural components in the production of emulsifier-free polyurethane dispersions
US3867171A (en) * 1972-11-24 1975-02-18 American Cyanamid Co Adhesive color printing system for floor coverings and other home furnishings fabrics
US3919351A (en) * 1973-08-29 1975-11-11 Ppg Industries Inc Composition useful in making extensible films
FR2247484B1 (en) * 1973-10-12 1978-05-26 Rhone Progil
US3832333A (en) * 1973-10-16 1974-08-27 Ppg Industries Inc Lactone reaction products
DE2437218C3 (en) * 1974-08-02 1980-12-04 Bayer Ag, 5090 Leverkusen Dihydroxysulfonates containing ether structures and processes for their preparation
DE2446440C3 (en) * 1974-09-28 1981-04-30 Bayer Ag, 5090 Leverkusen Process for the preparation of aqueous dispersions of polyurethanes containing sulfonate groups
US4108814A (en) * 1974-09-28 1978-08-22 Bayer Aktiengesellschaft Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols
US4066591A (en) * 1975-06-02 1978-01-03 Ppg Industries, Inc. Water-reduced urethane coating compositions
DE2551094A1 (en) * 1975-11-14 1977-05-26 Bayer Ag PROCESS FOR THE MANUFACTURING OF WATER DISPERSIBLE POLYURETHANES
DE2555534C3 (en) * 1975-12-10 1981-01-08 Bayer Ag, 5090 Leverkusen Polyurethanes dispersible in water
US4098743A (en) * 1976-05-26 1978-07-04 Ppg Industries, Inc. Polylactone-polyurethanes and aqueous dispersions thereof
US4147679A (en) * 1976-06-02 1979-04-03 Ppg Industries, Inc. Water-reduced urethane coating compositions
CA1131376A (en) * 1976-10-04 1982-09-07 David G. Hangauer, Jr. Aqueous urea-urethane dispersions
JPS5348740A (en) * 1976-10-15 1978-05-02 Ricoh Co Ltd Pressure sensitive adhesive electrostatic photographic toner
DE2651506C2 (en) * 1976-11-11 1986-04-30 Bayer Ag, 5090 Leverkusen Process for the preparation of water-dispersible polyurethanes
DE2816815A1 (en) * 1978-04-18 1979-10-31 Bayer Ag WATER DISPERSIBLE OR SOLUBLE POLYURETHANES AND A METHOD FOR THEIR MANUFACTURING
US4277380A (en) * 1979-03-29 1981-07-07 Textron, Inc. Water-dispersible urethane polymers and aqueous polymer dispersions
FR2470682A1 (en) * 1979-12-06 1981-06-12 Saint Gobain PROCESS FOR PRODUCING LAMINATES, LAMINATES OBTAINED AND GLUE USED THEREIN
FR2491018A2 (en) * 1980-03-21 1982-04-02 Esterel Caravanes Sa FOLDING CARAVAN INTERIOR FITTING
US4307219A (en) * 1980-04-30 1981-12-22 Minnesota Mining And Manufacturing Company Aqueous solvent dispersible linear polyurethane resins
DE3048085A1 (en) * 1980-12-19 1982-07-22 Bayer Ag, 5090 Leverkusen DISPERSIONS OF POLYMERS CONTAINING SULFONATE GROUPS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A COATING AGENT
DE3112117A1 (en) * 1981-03-27 1982-10-07 Bayer Ag, 5090 Leverkusen USE OF WATER DISPERSABLE POLYISOCYANATE PREPARATIONS AS ADDITIVES FOR AQUEOUS ADHESIVES
JPS5834878A (en) * 1981-08-25 1983-03-01 Sanyo Chem Ind Ltd Hot-melt type pressure-sensitive adhesive
US4460738A (en) * 1983-03-16 1984-07-17 Olin Corporation Preparation of carboxylic acid-containing polyurethane prepolymers and aqueous dispersions thereof
US4521615A (en) * 1983-03-16 1985-06-04 Olin Corporation Preparation of carboxylic acid-containing monoether and polyether polyol addition products
US4540633A (en) * 1983-04-20 1985-09-10 Textron, Inc. Water dispersible polyurethane adhesive compositions and adhesive layer formed therefrom
US4501852A (en) * 1983-06-20 1985-02-26 Mobay Chemical Corporation Stable, aqueous dispersions of polyurethane-ureas
DE3344693A1 (en) * 1983-12-10 1985-06-20 Bayer Ag, 5090 Leverkusen AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE-POLYADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS OR. FOR THE PRODUCTION OF ADHESIVES
DE3401753A1 (en) * 1984-01-19 1985-08-01 Bayer Ag, 5090 Leverkusen METHOD FOR THE PRODUCTION OF POLYURETHANES, POLYURETHANES WITH AROMATIC AMINO END GROUPS AND THE USE THEREOF
US4636546A (en) * 1984-03-29 1987-01-13 Rohm And Haas Company Process for preparing modified polymer emulsion adhesives
DE3438563A1 (en) * 1984-10-20 1986-04-24 Bayer Ag, 5090 Leverkusen AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE ADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A COATING OR SIZING AGENT FOR PAPER
US4576987A (en) * 1984-12-13 1986-03-18 Desoto, Inc. Aqueous water-repellent coatings
US4644030A (en) * 1985-02-01 1987-02-17 Witco Corporation Aqueous polyurethane - polyolefin compositions
DE3685867D1 (en) * 1985-09-16 1992-08-06 Vianova Kunstharz Ag METHOD FOR PRODUCING SELF-CROSSLINKING CATIONIC LACQUER.
GB8524579D0 (en) * 1985-10-04 1985-11-06 Polyvinyl Chemicals Inc Coating compositions
DE3540333A1 (en) * 1985-11-14 1987-05-21 Bayer Ag METHOD FOR IMMOBILIZING BIOLOGICAL MATERIAL, PARTICLE-SHAPED COAGULATES CONTAINING AN IMMOBILIZED BIOLOGICAL MATERIAL AND THEIR USE AS A CATALYST
US4748200A (en) * 1986-03-18 1988-05-31 Takeda Chemical Industries, Ltd. Thermosetting resins and electrodeposition coating compositions containing the same
US4663337A (en) * 1986-04-18 1987-05-05 E. R. Squibb & Sons, Inc. 7-oxabicycloheptane substituted amides useful in the treatment of thrombotic disease
DE3633421C1 (en) * 1986-10-01 1987-07-23 Goldschmidt Ag Th Polyoxyalkylene ethers containing hydroxyl and sulfonate groups and their use in the production of dispersible polyurethanes
DE3641494A1 (en) * 1986-12-04 1988-06-09 Bayer Ag POYLURETHANE SOLUBLE OR DISPERSABLE IN WATER, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COATING ANY SUBSTRATE
US4791168A (en) * 1987-04-15 1988-12-13 Basf Corporation, Inmont Division Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics
US4762880A (en) * 1987-05-05 1988-08-09 Uniroyal Plastics Co., Inc. Water-based thermoforming adhesives
EP0296098A3 (en) * 1987-06-16 1989-08-23 W.R. Grace & Co.-Conn. Crosslinked polyurethane emulsion, process and prepolymer for its production and process for forming coatings from said emulsion
DE3727252A1 (en) * 1987-08-15 1989-02-23 Bayer Ag METHOD FOR PRODUCING AQUEOUS POLYURETHANE DISPERSIONS
US4923756A (en) * 1987-08-20 1990-05-08 Ashland Oil, Inc. Primerless adhesive for fiberglass reinforced polyester substrates
DE3728140A1 (en) * 1987-08-22 1989-03-02 Bayer Ag AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE POLYADDITION PRODUCTS, A METHOD FOR PRODUCING THE AQUEOUS SOLUTIONS OR DISPERSIONS AND THEIR USE AS ADHESIVE
US5023309A (en) * 1987-09-18 1991-06-11 Rheox, Inc. Water dispersible, modified polyurethane thickener with improved high shear viscosity in aqueous systems
DE3738079A1 (en) * 1987-11-10 1989-05-18 Basf Lacke & Farben METHOD FOR PRODUCING MACROMONOMERS AND MACROMONOMERS PRODUCED BY THIS METHOD
US4883694A (en) * 1987-12-18 1989-11-28 Century Adhesives Corp. Method of forming flexible packages and novel flexible packages
US4851459A (en) * 1987-12-18 1989-07-25 Century Adhesives Corp. Aqueous peroxy carbamyl group containing polymer systems and methods of their production and use
US4876308A (en) * 1988-02-18 1989-10-24 Gencorp Inc. Polyurethane adhesive for a surface treatment-free fiber reinforced plastic
US4895894A (en) * 1988-05-31 1990-01-23 The Dow Chemical Company Modulus modification of water borne polyurethane-ureas
NO891754L (en) * 1988-06-02 1989-12-04 Minnesota Mining & Mfg NON-TREATIVE MOISTURIZING-CURING MIXTURES.
EP0369389A1 (en) * 1988-11-15 1990-05-23 Reichhold Chemicals, Inc. Water dispersible poly(urethaneureas) prepared with diisocyanate blends
US5039732A (en) * 1988-12-30 1991-08-13 The Sherwin-Williams Company Water-dispersable air-drying coatings
DE3903804C2 (en) * 1989-02-09 2001-12-13 Bollig & Kemper Aqueous paint dispersions and their use
US5124424A (en) * 1989-04-26 1992-06-23 Nippon Polyurethane Industry Co., Ltd. Polyurethane resin binder for magnetic recording mediums comprising a polycarbonate polyol
US4963637A (en) * 1989-06-23 1990-10-16 Union Carbide Chemicals And Plastics Company Inc. Acid containing isocyanate-terminated prepolymers, salt prepolymers and polymers thereof
US4954389A (en) * 1989-07-05 1990-09-04 Uniroyal Plastics Company, Inc. Multi-layer electrically conductive article
DE4011455A1 (en) * 1990-04-09 1991-10-10 Henkel Kgaa HOUSEHOLD ALL-PURPOSE GLUE BASED ON POLYURETHANE
DE4012630A1 (en) * 1990-04-20 1991-10-24 Bayer Ag Copolymer or graft copolymer with unsatd. per:fluoroalkyl monomer - and unsatd. per:fluoroalkyl-free monomer on dispersion of polyurethane contg. per:fluoroalkyl backbone, used as dressing
ES2033153T3 (en) * 1990-07-19 1993-03-01 Degussa Aktiengesellschaft MODIFIED SILICON DIOXIDE ON THE SURFACE.
DE4024567A1 (en) * 1990-08-02 1992-02-06 Basf Ag PRODUCTION OF AQUEOUS POLYURETHANE DISPERSIONS
US5155163A (en) * 1990-08-06 1992-10-13 Uniroyal Adhesives And Sealants, Inc. Aqueous polyurethane dispersion synthesis for adhesive thermoforming applications
DE4103347A1 (en) * 1991-02-05 1992-08-06 Bayer Ag WAFER POLYURETHANE DISPERSIONS AND THEIR USE AS CASCASING ADHESIVES
DE4109477A1 (en) * 1991-03-22 1992-09-24 Henkel Kgaa POLYMER DISPERSIONS SUITABLE FOR REACTIVE SYSTEMS
US5173526A (en) * 1991-04-26 1992-12-22 Air Products And Chemicals, Inc. Aqueous polyurethane-vinyl polymer dispersions for coating applications
DE4134064A1 (en) * 1991-10-15 1993-04-22 Bayer Ag BINDER COMBINATION, A METHOD FOR THEIR PRODUCTION AND THEIR USE
DE4137429A1 (en) * 1991-11-14 1993-05-19 Bayer Ag WAFEREN BINDER COMBINATION, A METHOD OF MANUFACTURING THEM AND THEIR USE
DE4222530A1 (en) * 1992-07-09 1994-01-13 Hoechst Ag Polyurethane dispersions
DE4227355A1 (en) * 1992-08-19 1994-02-24 Hoechst Ag Water-dilutable two-component coating compound
US5610232A (en) * 1993-09-24 1997-03-11 H.B. Fuller Licensing & Financing, Inc. Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
GB9400663D0 (en) * 1994-01-14 1994-03-09 Ucb Sa Aqueous polyurethane resin compositions
US5637639A (en) * 1994-09-09 1997-06-10 H.B. Fuller Licensing And Financing, Inc. Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0259679A1 (en) * 1986-09-04 1988-03-16 Bayer Ag Adhesive and the use of the adhesive in producing bonds
US4870129A (en) * 1986-09-04 1989-09-26 Bayer Aktiengesellschaft Adhesive and use of the adhesive for the formation of bonds
EP0368172A2 (en) * 1988-11-08 1990-05-16 Toyo Boseki Kabushiki Kaisha A magnetic recording medium
DE3930352A1 (en) * 1989-09-12 1991-03-21 Renia Gmbh Bonding shoe parts, esp. for shoe repair - by applying solvent-free polyurethane dispersion adhesive and drying in microwave oven before bringing parts together
WO1995008583A1 (en) * 1993-09-24 1995-03-30 H.B. Fuller Licensing & Financing, Inc. Aqueous anionic polyurethane dispersions
EP0666275A2 (en) * 1994-02-08 1995-08-09 Air Products And Chemicals, Inc. Organic solvent free urethane/acrylic polymer laminating adhesive for flexible packaging
US5455293A (en) * 1994-06-06 1995-10-03 Wood; Benny R. Water dispersible polyurethane adhesive
WO1996007540A1 (en) * 1994-09-09 1996-03-14 H.B. Fuller Licensing And Financing, Inc. Aqueous polyurethane dispersion adhesive compositions with improved heat resistance

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717025A (en) * 1996-09-16 1998-02-10 H. B. Fuller Licensing & Financing, Inc. Melamine-formaldehyde resin based adhesive compositions
US6180244B1 (en) 1998-02-17 2001-01-30 3M Innovative Properties Company Waterbased thermoforming adhesives
KR100528122B1 (en) * 1998-12-30 2006-01-27 에스케이케미칼주식회사 Water based polyurethane adhesive composition
US6306942B1 (en) 2000-04-05 2001-10-23 3M Innovative Properties Company Low temperature thermally activated water-dispersed adhesives
US6310125B1 (en) 2000-04-05 2001-10-30 3M Innovative Properties Company Water-dispersed adhesive compositions
US6444737B1 (en) 2000-04-05 2002-09-03 3M Innovative Properties Company Water-dispersed polymer stabilizer
US6541550B1 (en) 2000-04-05 2003-04-01 3M Innovative Properties Company Low temperature thermally activated water-dispersed adhesive compositions
EP1382622A1 (en) 2002-07-19 2004-01-21 Dainippon Ink And Chemicals, Inc. Aqueous polyurethane resin dispersion and aqueous adhesive
CN1300207C (en) * 2002-07-19 2007-02-14 大日本油墨化学工业株式会社 Polyurethane resin liquid disperse colloid and liquid adhesives
US7294670B2 (en) 2002-07-19 2007-11-13 Dainippon Ink And Chemicals, Inc. Aqueous polyurethane resin dispersion and aqueous adhesive
KR100880827B1 (en) * 2002-07-19 2009-01-30 디아이씨 가부시끼가이샤 Polyurethane Resin Aqueous Dispersion and Aqueous Adhesive
WO2012069412A1 (en) * 2010-11-26 2012-05-31 Bayer Materialscience Ag Use of aqueous dispersions as primers
CN108102443A (en) * 2010-11-26 2018-06-01 科思创德国股份有限公司 Use of aqueous dispersions as primers

Also Published As

Publication number Publication date
US5872182A (en) 1999-02-16
EP0847409A1 (en) 1998-06-17
TW349961B (en) 1999-01-11
AR004275A1 (en) 1998-11-04
NZ310252A (en) 2000-01-28
CA2233083A1 (en) 1997-05-29

Similar Documents

Publication Publication Date Title
US5872182A (en) Water-based polyurethanes for footwear
KR100209563B1 (en) Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
US5610232A (en) Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
CN108250390B (en) A kind of water dispersion of polyurethane or polyurethane-urea, preparation method and use
AU695629B2 (en) Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
US5432228A (en) Aqueous solutions and dispersions of polyisocyanate polyaddition products, a process for the production of the aqueous solutions and dispersions and their use as adhesives
US5637639A (en) Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance
US4946535A (en) Polyester polyurethanes containing hydroxyl end groups and their use as adhesives
MXPA97001745A (en) Adhesive compositions of aqueous dispersions depoliuretano with improved resistance to the ac
EP2766405B1 (en) Cold contact adhesives
CZ293188B6 (en) Water-based adhesive formulation having enhanced characteristics
JPS6134729B2 (en)
JP2003306523A (en) Solventless moisture-curable hot melt urethane resin composition, foam, and sheet structure using the same
CN112979900B (en) Aqueous polyurethane or polyurethane-urea dispersions, method for the production thereof and use thereof
EP1735361B1 (en) Adhesive aqueous compositions
AU712956B2 (en) Improved water-based polyurethanes for footwear
JPH0588757B2 (en)
JP2003335836A (en) Aqueous dispersion of polyurethane resin and aqueous adhesive
CA2101389A1 (en) Anionically modified polyurethane ureas having reduced tackiness for the coating of leather
CN109971016A (en) Coated product or article and method of manufacture
MXPA97002780A (en) Reduced solvent process for the preparation of polyurethane dispersions with improved heat resistance and solvent

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN MX NZ

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 310252

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 1996918326

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2233083

Country of ref document: CA

Ref country code: CA

Ref document number: 2233083

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1996918326

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996918326

Country of ref document: EP