USA - Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
- Google Patents
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
Download PDF
Info
- Publication number
- USA
USA
US08/304,653
USA
USA
US A
US A
US A
US A
US A
US A
US A
US A
US A
- Authority
- US
- United States
- Prior art keywords
- dispersion
- acid
- heat resistance
- adhesive
- molecular weight
- Prior art date
- -09-24
- 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.)
-
Expired - Fee Related
Application number
US08/304,653
Inventor
Youlu Duan
Sonja Stammler
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.)
-09-24
Filing date
-09-09
Publication date
-03-04
-09-09
Application filed by HB Fuller Licensing and Financing Inc
filed
Critical
HB Fuller Licensing and Financing Inc
-09-09
Priority to US08/304,653
priority
Critical
patent/USA/en
-11-22
Priority to US08/343,676
priority
patent/USA/en
-11-28
Assigned to H.B. FULLER LICENSING & FINANCING, INC.
reassignment
H.B. FULLER LICENSING & FINANCING, INC.
ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS).
Assignors: STAMMLER, SONJA, DUAN, YOULU
-01-04
Priority to CAA
priority
patent/CAA1/en
-01-04
Priority to EST
priority
patent/EST3/en
-01-04
Priority to JPA
priority
patent/JPB2/en
-01-04
Priority to KRA
priority
patent/KRB1/en
-01-04
Priority to PCT/US/
priority
patent/WOA1/en
-01-04
Priority to EPA
priority
patent/EPB1/en
-01-04
Priority to NZA
priority
patent/NZA/en
-01-04
Priority to MXA
priority
patent/MXA/en
-01-04
Priority to ATT
priority
patent/ATET1/en
-01-04
Priority to AU/95A
priority
patent/AUB2/en
-01-04
Priority to DET
priority
patent/DET2/en
-06-07
Priority to US08/480,780
priority
patent/USA/en
-09-15
Priority to US08/528,936
priority
patent/USA/en
-11-21
Priority to US08/561,197
priority
patent/USA/en
-03-04
Publication of USA
publication
Critical
patent/USA/en
-03-04
Application granted
granted
Critical
-03-04
Anticipated expiration
legal-status
Critical
Status
Expired - Fee Related
legal-status
Critical
Current
Links
-
USPTO
-
USPTO PatentCenter
-
USPTO Assignment
-
Espacenet
-
Global Dossier
-
Discuss
Classifications
-
-
B'PERFORMING OPERATIONS; TRANSPORTING
-
B32'LAYERED PRODUCTS
-
B32B'LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
-
B32B15/00'Layered products comprising a layer of metal
-
B32B15/04'Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
B32B15/08'Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
-
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
-
-
B'PERFORMING OPERATIONS; TRANSPORTING
-
B32'LAYERED PRODUCTS
-
B32B'LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
-
B32B21/00'Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
-
B32B21/04'Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
B32B21/08'Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
-
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/'Manufacture of polymers containing ionic or ionogenic groups
-
C08G18/'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/'Manufacture of polymers containing ionic or ionogenic groups
-
C08G18/'Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
C08G18/'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/'Manufacture of polymers containing ionic or ionogenic groups
-
C08G18/'Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
C08G18/'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/'Manufacture of polymers in the presence of non-reactive compounds
-
C08G18/'Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
-
C08G18/'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/'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/'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/'Compounds of group C08G18/42
-
C08G18/'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
-
C08G/00'Compositions for adhesives
-
C08G/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
-
C08G/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/'Composite [nonstructural laminate]
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'Next to addition polymer of ethylenically unsaturated monomer
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'Next to addition polymer of ethylenically unsaturated monomer
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'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/'Composite [nonstructural laminate]
-
Y10T428/'Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
Y10T428/'Next to free metal
Definitions
-
This invention
relates new aqueous polyurethane dispersion adhesive compositions which can be an one component or a two component for use in thermoforming. More particularly, this invention relates to aqueous polyurethane dispersion adhesive compositions comprising carboxylic acid and/or its salt-containing sulfonated polyurethane dispersions, and with or without compatible crosslinking agents. These new adhesive compositions exhibit good stability at low pH values, long pot life, high green strength, good water resistance and improved heat resistance.
-
Aqueous dispersions of polyurethanes
are known and are described in, for example, U.S. Pat. No. 3,479,310; Angew. Chem., 82, 53, (); and Angew. Makromol. Chem., 98, ().
-
the ionic salt groups
are salts of carboxylic acid or sulfonic acid.
-
Aqueous polyurethanes having only internal carboxylate groups as anionic moieties
are stable only at pH>7.
-
Such polyurethane dispersions
can form a two component adhesive composition with a compatible crosslinker, such as polyfunctional isocyanates, epoxies or aziridines.
-
thermoforming adhesives
comprising aromatic polyurethanes, cross-linking agents and others. These kind of adhesive compositions will need high temperature to activate due to the aromatic polyurethane component.
-
U.S. Pat. No. 4,870,129 to Henning et al
discloses an adhesive consisting of an aqueous polyurethane containing chemically incorporated carboxylate or sulfonate groups.
-
the adhesive of this reference
showed low activation temperature but only medium heat resistance.
-
the present invention
is directed to novel aqueous sulfonated polyurethane dispersions having low activation temperatures, long pot-life and high heat resistance, even without addition of a crosslinker at the time of use.
-
the aqueous polyurethane dispersion adhesive compositions of the invention
have good compatibility with other water based polymers, such as other aqueous polyurethane dispersions either sulfonated or carboxylated polyurethane dispersions, vinyl acetate emulsions and acrylate emulsions, and also have good compatibility with thickening agents and pigments.
-
compositions of the invention
are aqueous dispersions of an anionic polyurethane, the polyurethane comprising the reaction product of an isocyanate terminated polyurethane prepolymer, and a chain extender, the polyurethane prepolymer comprising the reaction product of a polyol component and a diisocyanate component, the polyol component comprising:
-
(R)
represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, and
-
a low molecular weight aliphatic diol
having a molecular weight of from 60 to 400.
-
the dispersions of the invention
may be utilized with or without a compatible crosslinker, such as polyfunctional aziridine, zinc ammonium carbonate or zirconium carbonate.
-
a compatible crosslinker
such as polyfunctional aziridine, zinc ammonium carbonate or zirconium carbonate.
-
even the uncrosslinked adhesives
provide equivalent or better heat resistance than prior art dispersions to which a cross-linker has been added at the time of use.
-
Molecular weights referred to herein
are number average molecular weights.
-
the isocyanate terminated polyurethane prepolymer used in the dispersions of the invention
are reaction products of a polyol mixture and a polyisocyanate.
-
the polyol mixture
comprises a sulfonated polyester polyol, a hydroxy carboxylic acid and a low molecular weight diol.
-
the sulfonated polyester polyols used to form the isocyanate terminated polyurethane prepolymer
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
may be in acid or salt form. Suitable salt forms are alkali metal salts, or tertiary amine salts.
-
Typical 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.
-
the non-sulfonated diacids
include adipic, azelaic, succinic, suberic and phthalic acids.
-
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-1,3 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.
-
the preferred sulfonated polyester polyols
are based on 5-sulfoisophthalic acid monosodium salt, 1,6-hexanediol and adipic acid.
-
Examples of preferred conunercially available sulfonated polyester polyols
are Rucoflex XS--55 and Rucoflex XS--60, made by Ruco Polymer Corporation. These sulfonated polyester polyols are based on 5-sulfoisophthalic acid monosodium salt (4 wt. % in XS--55, and 6 wt. % in XS--60), 1,6-hexanediol and adipic acid.
-
the sulfonated polyester polyols
desirably will have a molecular weight in the range of about 500 to 10,000 and a melting temperature in the range of about 10° to 100° C.
-
the preferred molecular weight range
is about 1,000 to 4,000 and the preferred melting temperature is between 30° C. and 80° C., more preferably between 40° C. and 60° C.
-
hydroxy carboxylic acids used to form the isocyanate terminated polyurethane prepolymer
are compounds of the formula:
-
the hydroxy carboxylic acids
are ' , ' -dimethylol alkanoic acids represented by the formula: ##STR1## where R 1 denotes hydrogen or an alkyl group with up to 9 carbon atoms. Examples of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanic acid.
-
the preferred dihydroxyalkanoic acid
is 2,2-dimethylolpropionic acid (DMPA).
-
the low molecular weight diols used in forming the isocyanate terminated polyurethane prepolymer
are aliphatic diols, particularly alkylene diols. Their molecular weight range is from 60 to 400.
-
the low molecular weight diols
are C 2 -C 8 alkylene diols and most preferably C 3 -C 6 alkylene diols examples of the diols are ethylene glycol, 1,3-propylene glycol, 1,4-butanediol (1,4-BD) and 1,6-hexanediol.
-
the diisocyanates which are used in forming the isocyanate terminated polyurethane prepolymer
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
tetramethylxy
-
aromatic diisocyanates
examples include phenylenediisocyanate, tolylenediisocyanate (TDI), xylylenediisocyanate, biphenylenediisocyanate, naphthylenediisocyanate and diphenylmethanediisocyanate (MDI).
-
the polyurethane prepolymer
is desirably formed in the presence of a water compatible solvent such as 1-methyl-2-pyrrolidone (NMP), dipropylene glycol methyl ether acetate (DPMA), or acetone.
-
NMP
1-methyl-2-pyrrolidone
-
DPMA
dipropylene glycol methyl ether acetate
-
acetone
the amount of solvent used is suitably in the range of 3-15% of the final polyurethane dispersion.
-
acetone
after dispersing and chain extending of the prepolymer, the acetone is then distilled off so that the final level of acetone may be as little as 1.0% or even less without disrupting the stability of the dispersion.
-
the prepolymer
After the prepolymer is formed, it is dispersed in water. To accomplish dispersion, the sulfonate groups, if not already in salt form, and at least a portion of the carboxylic acid groups of the prepolymer are neutralized with a tertiary amine.
-
the tertiary amine
may be added with the water, but more preferably neutralization is accomplished before the water is added, suitably by direct addition to the prepolymer/solvent mixture.
-
the isocyanate terminated prepolymer
is chain extended and terminated by reaction with primary or secondary amine functional compounds.
-
the chain extenders used
are preferably water soluble compounds as these increase the dispersibility of the polymer end product in water.
-
Organic diamines
are preferably used because they generally provide the maximum increase in molecular weight without causing gelling of the polyurethane dispersion.
-
Useful chain extenders
include aliphatic, cycloaliphatic, and aromatic diamines.
-
Suitable diamines
are ethylenediamine (EDA), propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethyldiamine, hexamethylenediamine (HDI), N-methylpropylenediamine, diaminophenylsulfone, diaminodiphenylether, diaminodiphenyldimethylmethane, 2,4-diamino-6-phenyltriazine, isophoronediamine, dimer fatty acid diamine, N-isodecycloxy propyl-1,3-diaminopropane and imidazolidinone functional diamines.
-
EDA
ethylenediamine
-
propylenediamine
propylenediamine
-
1,4-butylenediamine
piperazine
-
1,4-cyclohexyldimethyldiamine
1,4-butylenediamine
-
HDI
hexamethylenediamine
-
chain terminators
examples include aminoalcohols, like ethanolamine, propanolamine, butanolamine, N-methylethanolamine, N-methylisopropanolamine, taurine and isethionic acid.
-
compositions of the invention
may be crosslinked by adding a crosslinker to the dispersion at, or shortly before, the time it is applied to a substrate and dried.
-
Crosslinking
may be accomplished with conventional dispersable polyisocyanate crosslinkers.
-
these
are not preferred as optimal crosslinking performance requires a relatively high level of terminal primary or secondary amine groups in the aqueous polyurethane dispersions of the invention and therefore a correspondingly high level of diamine chain extender used in the chain extension/termination reaction.
-
the more amine used
the more difficult it is to maintain a stable dispersion and reduce the pot-life of the dispersion after addition of the polyisocyanate crosslinker.
-
the carboxylate groups introduced into the sulfonated polyurethane polymer via the hydroxy carboxylic acid component of the polyol component
are employed as crosslinking sites.
-
the carboxylate groups
are reacted with carboxylic acid reactive crosslinkers active at room temperature, such as polyfunctional aziridine compounds, zinc ammonium carbonate, zirconium carbonate or polyfunctional carbodiimide compounds.
-
aqueous polyurethane dispersion adhesive compositions of the present invention
when compounded with a compatible carboxylic acid reactive crosslinker have improved heat resistance, good water resistance, and longer pot-life than obtained with conventional dispersable isocyanate crosslinkers.
-
crosslinkers
are added at a level of 1-10% by weight.
-
the heat resistance of the aqueous polyurethane dispersions
is significantly improved by the employment of the low molecular weight diol in forming the polyurethane prepolymer.
-
the heat resistance of the polyurethane polymer
is so greatly improved by the low molecular weight diol that one component adhesive compositions used without crosslinker, in preferred embodiments of the invention, give better high temperature resistance than commercial prior art dispersion adhesives employing crosslinkers.
-
the dispersion adhesive
with or without crosslinker, is applied to a film web substrate and dried, after which it is heated and the second film web substrate applied.
-
the temperature of heating
referred to in the art as the activation temperature, is selected to provide good tack so the adhesive bonds to the second web and to change the physical properties of the adhesive by increasing the physical or chemical crosslinks so that the adhesive after heating provides a higher heat resistance, and usually higher water and solvent resistance, than before heating. Higher temperatures are frequently required to accomplish a desired change in adhesive heat resistance properties than to merely assure good adhesive wetting.
-
aqueous polyurethane dispersion adhesives
not only give high heat resistance, but also do so at low heat activation temperatures. Activation temperatures as low as 125° F. have been shown to effectively implement the heat resistance properties of the inventive formulations, even without crosslinker.
-
the aqueous polyurethane dispersions of the invention
also have small particle sizes and excellent stability over a large pH range (3-11).
-
a one-component composition substantially as in Example 13 below
may be used in automobiles, bonding polypropylene foam to polyvinyl chloride at activation temperature of about 215° F.; in aerospace, bonding of DuPont Tedlar® PVF to phenolic composite at activation temperatures in the range of from room temperature to 210° F.; in shoemaking, bonding leather to SBR (activation temperature 150°-170° F.), and bonding highly plasticized PVC to itself or other substrates (activation temperature 150°-170° F.); in woodworking, bonding PVC to medium density fiberboard (activation temperature 150° F.); in bookbinding, bonding paper to paper using activation temperatures from room temperature to 200° F.; in house siding for bonding Tedlar® to PVC, wood
-
the formulations of the invention
have good compatibility with other water based polymer dispersions even those having low pH (pH 4-7). This compatibility makes the formulations of the invention useful in blends with acrylic, epoxy and vinyl acetate or other vinyl polymer dispersions, as well as other polyurethane polymer dispersions. Blends with water based acrylic polymers can be used for shoe and fiberglass sizing applications. Blends with vinyl acetate or other vinyl polymer dispersions have use in automotive, woodworking, and bookbinding applications.
-
a 100 g weight
was attached to each PVC bond in a T-peel configuration and then placed in the Tenney oven.
-
the T-peels
had a 1 square inch bond area.
-
the T-peels
were subjected to a 25° C. increase in temperature each hour until 125° C. The temperatures and the times were recorded by the Tenney sensing unit upon bond failure.
-
the Rucoflex XS--55
was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C.
-
the DMPA, TMXDI and HDI
were added, whereupon the temperature was maintained at about 80° F. for 3 hours and then cooled to about 65°-70° C. At this temperature, the TEA was added and stirred for 10-15 minutes. The temperature was further reduced to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA. A finely divided dispersion having a solids content of 32.0% and a pH of 8.5 was obtained.
-
the method for preparing the dispersion of Example 2
was the same as the method for Example 1 except that the 1,4-BD was added at the same time as the DMPA. A finely divided dispersion having a solids content of 31.4% and a pH of 7.95 was obtained.
-
compositions
were prepared as shown in Table 1.
-
the preparation method for Examples 3-5
was the same as the method of Examples 1-2 except that IPDI was used instead of TMXDI.
-
the Rucoflex XS--55
was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C.
-
the DMPA, 1,4-BD, TMXDI and HDI
were added, whereupon the temperature was maintained at about 80° C. for 3 hours and then cooled to 65°-70° C. At this temperature, the TEA was added and stirred for 10-15 minutes. The temperature was further cooled to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA.
-
a finely divided dispersion having a solids content of 31.4% and a pH of 7.3
was obtained. This dispersion had good water resistance and high heat resistance and could be used as a one-component adhesive.
-
the dispersion preparation method Examples 7-14
was the same as the method of Example 6 except for the use of IPDI instead of TMXDI in Examples 8-14 and the use of acetone solvent in Examples 13-14 in place of NMP solvent.
-
the testing results of the heat resistance
are shown in Table 4.
-
formulations of Disperecoll KA , an aqueous polyurethane dispersion product of Bayer Corporation, based on HDI and IPDI (Formulation B), and of an embodiment of the sulfonated polyester containing polyurethane dispersion invention of copending application Ser. No. 08/126,508, filed Sep. 24, (Formulation A),
were prepared and tested for heat resistance in one component and two-component compositions, the second component being a commercial polyisocyanate crosslinker.
-
the crosslinker employed
was Desmodur DA (Bayer, a dispersible polyisocyanate based on trimer of hexamethylenediisocyanate).
-
the sulfonated polyester containing polyurethane dispersion, Formulation A
was prepared from the following ingredients:
-
TXDI
tetramethylxylylene diisocyanate
-
Heat resistance
was determined as in the previous examples.
-
Films made from the one-component aqueous polyurethane dispersions of Examples 8-14
were immersed in water for 7 days, after which they had not changed. Films made from KA- in Example 15 (uncrosslinked), by contrast, had totally lost their strength after immersing in water for only 1 day.
-
the Rucoflex XS--55
was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C.
-
the DMPA, 1,4-BD, and IPDI
were added, whereupon the temperature was maintained at about 85° C. for 3 hours and then cooled to 65°-70° C. At this temperature, the TEA was added and stirred for 10-13 minutes. The temperature was further cooled to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA.
-
Crosslinkers used
were 5% by weight Desmondur DA and 2% by weight CX-100. Heat resistance was determined as in the previous examples. Results are shown in Table 6.
Landscapes
-
Chemical & Material Sciences
(AREA)
-
Organic Chemistry
(AREA)
-
Health & Medical Sciences
(AREA)
-
Chemical Kinetics & Catalysis
(AREA)
-
Medicinal Chemistry
(AREA)
-
Polymers & Plastics
(AREA)
-
Engineering & Computer Science
(AREA)
-
Manufacturing & Machinery
(AREA)
-
Dispersion Chemistry
(AREA)
-
General Chemical & Material Sciences
(AREA)
-
Life Sciences & Earth Sciences
(AREA)
-
Wood Science & Technology
(AREA)
-
Polyurethanes Or Polyureas
(AREA)
-
Adhesives Or Adhesive Processes
(AREA)
-
Compositions Of Macromolecular Compounds
(AREA)
-
Laminated Bodies
(AREA)
Abstract
Aqueous dispersion adhesives of anionic polyurethanes which have high heat resistance and low activation temperature, even when employed without addition of a crosslinker. The polyurethane is the reaction product of an isocyanate terminated polyurethane prepolymer, and a chain extender. The polyurethane prepolymer is the reaction product of a polyol component and a diisocyanate component, the polyol component including:
a sulfonated polyester polyol,
a hydroxy carboxylic acid of the formula:
(HO).sub.x R(COOH).sub.y
wherein (R) represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, and
a low molecular weight aliphatic diol having a molecular weight of from 60 to 400.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of Ser. No. 08/126,508, filed Sep. 24, , now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates new aqueous polyurethane dispersion adhesive compositions which can be an one component or a two component for use in thermoforming. More particularly, this invention relates to aqueous polyurethane dispersion adhesive compositions comprising carboxylic acid and/or its salt-containing sulfonated polyurethane dispersions, and with or without compatible crosslinking agents. These new adhesive compositions exhibit good stability at low pH values, long pot life, high green strength, good water resistance and improved heat resistance.
2. Description of the Prior Art
Aqueous dispersions of polyurethanes are known and are described in, for example, U.S. Pat. No. 3,479,310; Angew. Chem., 82, 53, (); and Angew. Makromol. Chem., 98, ().
U.S. Pat. No. 3,479,310 to Dieterich et al discloses dispersing in water a fully chain extended, NCO-free polyurethane having internal ionic salt groups.
For anionic aqueous polyurethane dispersions, the ionic salt groups are salts of carboxylic acid or sulfonic acid.
Aqueous polyurethanes having only internal carboxylate groups as anionic moieties are stable only at pH>7. Such polyurethane dispersions can form a two component adhesive composition with a compatible crosslinker, such as polyfunctional isocyanates, epoxies or aziridines.
Henning, et al., U.S. Pat. No. 4,870,129, discloses use of the sodium salt of N-(2-aminoethyl)-2-aminoethane sulfonate acid (AAS salt) to prepare polyurethane dispersions. The aqueous polyurethane dispersions are reported to have exhibited good stability at low pH values (5-7), high green strength and medium heat resistance.
Usually, after blending the sulfonated polyurethane dispersions with a polyisocyanate crosslinker, such as the dispersible polyisocyanate in U.S. Pat. No. 4,663,377 to Hombach et al, their heat resistance will be improved.
Leung, U.S. Pat. No. 4,762,880, discloses water-based thermoforming adhesives comprising aromatic polyurethanes, cross-linking agents and others. These kind of adhesive compositions will need high temperature to activate due to the aromatic polyurethane component.
U.S. Pat. No. 4,870,129 to Henning et al discloses an adhesive consisting of an aqueous polyurethane containing chemically incorporated carboxylate or sulfonate groups. The adhesive of this reference showed low activation temperature but only medium heat resistance.
Duan et al in copending application Ser. No. 08/126,508, filed Sep. 24, , disclose aqueous polyurethane dispersions based on sulfonated polyester polyols, which have an unusually high crystallization rate, while also exhibiting good stability at low pH values, high green strength and medium heat resistance.
SUMMARY OF THE INVENTION
The present invention is directed to novel aqueous sulfonated polyurethane dispersions having low activation temperatures, long pot-life and high heat resistance, even without addition of a crosslinker at the time of use. The aqueous polyurethane dispersion adhesive compositions of the invention have good compatibility with other water based polymers, such as other aqueous polyurethane dispersions either sulfonated or carboxylated polyurethane dispersions, vinyl acetate emulsions and acrylate emulsions, and also have good compatibility with thickening agents and pigments.
The compositions of the invention are aqueous dispersions of an anionic polyurethane, the polyurethane comprising the reaction product of an isocyanate terminated polyurethane prepolymer, and a chain extender, the polyurethane prepolymer comprising the reaction product of a polyol component and a diisocyanate component, the polyol component comprising:
a sulfonated polyester polyol,
a hydroxy carboxylic acid of the formula:
(HO).sub.x R(COOH).sub.y
wherein (R) represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, and
a low molecular weight aliphatic diol having a molecular weight of from 60 to 400.
The dispersions of the invention may be utilized with or without a compatible crosslinker, such as polyfunctional aziridine, zinc ammonium carbonate or zirconium carbonate. In their preferred embodiments, even the uncrosslinked adhesives provide equivalent or better heat resistance than prior art dispersions to which a cross-linker has been added at the time of use.
DETAILED DESCRIPTION OF THE INVENTION
Molecular weights referred to herein are number average molecular weights.
The isocyanate terminated polyurethane prepolymer used in the dispersions of the invention are reaction products of a polyol mixture and a polyisocyanate. The polyol mixture comprises a sulfonated polyester polyol, a hydroxy carboxylic acid and a low molecular weight diol.
The sulfonated polyester polyols used to form the isocyanate terminated polyurethane prepolymer 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 may be in acid or salt form. Suitable salt forms are alkali metal salts, or tertiary amine salts. 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-1,3 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 preferred sulfonated polyester polyols are based on 5-sulfoisophthalic acid monosodium salt, 1,6-hexanediol and adipic acid. Examples of preferred conunercially available sulfonated polyester polyols are Rucoflex XS--55 and Rucoflex XS--60, made by Ruco Polymer Corporation. These sulfonated polyester polyols are based on 5-sulfoisophthalic acid monosodium salt (4 wt. % in XS--55, and 6 wt. % in XS--60), 1,6-hexanediol and adipic acid.
The sulfonated polyester polyols desirably will have a molecular weight in the range of about 500 to 10,000 and a melting temperature in the range of about 10° to 100° C. The preferred molecular weight range is about 1,000 to 4,000 and the preferred melting temperature is between 30° C. and 80° C., more preferably between 40° C. and 60° C.
The hydroxy carboxylic acids used to form the isocyanate terminated polyurethane prepolymer are compounds of the formula:
(HO).sub.x R(COOH).sub.y
wherein R represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3. Preferably, the hydroxy carboxylic acids are α,α-dimethylol alkanoic acids represented by the formula: ##STR1## where R1 denotes hydrogen or an alkyl group with up to 9 carbon atoms. Examples of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanic acid. The preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid (DMPA).
The low molecular weight diols used in forming the isocyanate terminated polyurethane prepolymer are aliphatic diols, particularly alkylene diols. Their molecular weight range is from 60 to 400. Preferably, the low molecular weight diols are C2 -C8 alkylene diols and most preferably C3 -C6 alkylene diols examples of the diols are ethylene glycol, 1,3-propylene glycol, 1,4-butanediol (1,4-BD) and 1,6-hexanediol.
The diisocyanates which are used in forming the isocyanate terminated polyurethane prepolymer 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).
The polyurethane prepolymer is desirably formed in the presence of a water compatible solvent such as 1-methyl-2-pyrrolidone (NMP), dipropylene glycol methyl ether acetate (DPMA), or acetone. In the case where NMP or DPMA are used the amount of solvent used is suitably in the range of 3-15% of the final polyurethane dispersion. In the case where acetone is used, after dispersing and chain extending of the prepolymer, the acetone is then distilled off so that the final level of acetone may be as little as 1.0% or even less without disrupting the stability of the dispersion.
After the prepolymer is formed, it is dispersed in water. To accomplish dispersion, the sulfonate groups, if not already in salt form, and at least a portion of the carboxylic acid groups of the prepolymer are neutralized with a tertiary amine. The tertiary amine may be added with the water, but more preferably neutralization is accomplished before the water is added, suitably by direct addition to the prepolymer/solvent mixture.
In the aqueous dispersion the isocyanate terminated prepolymer is chain extended and terminated by reaction with primary or secondary amine functional compounds. The chain extenders used are preferably water soluble compounds as these increase the dispersibility of the polymer end product in water. Organic diamines are preferably used because they generally provide the maximum increase in molecular weight without causing gelling of the polyurethane dispersion. Useful chain extenders include aliphatic, cycloaliphatic, and aromatic diamines. Examples of suitable diamines are ethylenediamine (EDA), propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethyldiamine, hexamethylenediamine (HDI), N-methylpropylenediamine, diaminophenylsulfone, diaminodiphenylether, diaminodiphenyldimethylmethane, 2,4-diamino-6-phenyltriazine, isophoronediamine, dimer fatty acid diamine, N-isodecycloxy propyl-1,3-diaminopropane and imidazolidinone functional diamines.
Examples of useful chain terminators include aminoalcohols, like ethanolamine, propanolamine, butanolamine, N-methylethanolamine, N-methylisopropanolamine, taurine and isethionic acid.
The compositions of the invention may be crosslinked by adding a crosslinker to the dispersion at, or shortly before, the time it is applied to a substrate and dried. Crosslinking may be accomplished with conventional dispersable polyisocyanate crosslinkers. However these are not preferred as optimal crosslinking performance requires a relatively high level of terminal primary or secondary amine groups in the aqueous polyurethane dispersions of the invention and therefore a correspondingly high level of diamine chain extender used in the chain extension/termination reaction. Generally, the more amine used, the more difficult it is to maintain a stable dispersion and reduce the pot-life of the dispersion after addition of the polyisocyanate crosslinker. Therefore, in a preferred embodiment of this invention, the carboxylate groups introduced into the sulfonated polyurethane polymer via the hydroxy carboxylic acid component of the polyol component are employed as crosslinking sites. The carboxylate groups are reacted with carboxylic acid reactive crosslinkers active at room temperature, such as polyfunctional aziridine compounds, zinc ammonium carbonate, zirconium carbonate or polyfunctional carbodiimide compounds.
It has been found that the aqueous polyurethane dispersion adhesive compositions of the present invention when compounded with a compatible carboxylic acid reactive crosslinker have improved heat resistance, good water resistance, and longer pot-life than obtained with conventional dispersable isocyanate crosslinkers. Typically crosslinkers are added at a level of 1-10% by weight.
It has also been found in this invention that the heat resistance of the aqueous polyurethane dispersions is significantly improved by the employment of the low molecular weight diol in forming the polyurethane prepolymer. In fact the heat resistance of the polyurethane polymer is so greatly improved by the low molecular weight diol that one component adhesive compositions used without crosslinker, in preferred embodiments of the invention, give better high temperature resistance than commercial prior art dispersion adhesives employing crosslinkers.
The high heat resistance benefits are obtained with low activation temperature. In film bonding use, the dispersion adhesive, with or without crosslinker, is applied to a film web substrate and dried, after which it is heated and the second film web substrate applied. The temperature of heating, referred to in the art as the activation temperature, is selected to provide good tack so the adhesive bonds to the second web and to change the physical properties of the adhesive by increasing the physical or chemical crosslinks so that the adhesive after heating provides a higher heat resistance, and usually higher water and solvent resistance, than before heating. Higher temperatures are frequently required to accomplish a desired change in adhesive heat resistance properties than to merely assure good adhesive wetting. Unexpectedly, it has been found that the preferred one component aqueous polyurethane dispersion adhesives not only give high heat resistance, but also do so at low heat activation temperatures. Activation temperatures as low as 125° F. have been shown to effectively implement the heat resistance properties of the inventive formulations, even without crosslinker.
In accordance with the invention, the aqueous polyurethane dispersions of the invention also have small particle sizes and excellent stability over a large pH range (3-11).
The high green strength and high heat resistance at low activation temperature makes the one-component or two-component compositions of the invention particularly useful in automotive, aerospace, shoe material bonding, woodworking, bookbinding, fiberglass sizing and film laminating applications. For instance, a one-component composition substantially as in Example 13 below, may be used in automobiles, bonding polypropylene foam to polyvinyl chloride at activation temperature of about 215° F.; in aerospace, bonding of DuPont Tedlar® PVF to phenolic composite at activation temperatures in the range of from room temperature to 210° F.; in shoemaking, bonding leather to SBR (activation temperature 150°-170° F.), and bonding highly plasticized PVC to itself or other substrates (activation temperature 150°-170° F.); in woodworking, bonding PVC to medium density fiberboard (activation temperature 150° F.); in bookbinding, bonding paper to paper using activation temperatures from room temperature to 200° F.; in house siding for bonding Tedlar® to PVC, wood, wood composite, recycled wood and/or paper products; and in laminating of films of polyethylene terephthalate to films of polypropylene, polyethylene or aluminum or other metal foils (activation temperatures of 125°-150° F.).
The formulations of the invention have good compatibility with other water based polymer dispersions even those having low pH (pH 4-7). This compatibility makes the formulations of the invention useful in blends with acrylic, epoxy and vinyl acetate or other vinyl polymer dispersions, as well as other polyurethane polymer dispersions. Blends with water based acrylic polymers can be used for shoe and fiberglass sizing applications. Blends with vinyl acetate or other vinyl polymer dispersions have use in automotive, woodworking, and bookbinding applications.
The invention is further illustrated, by the following non-limiting examples in which all pans and percentages are by weight unless otherwise specified.
EXAMPLES
Heat resistance
Drawdown polyurethane dispersion with or without a crosslinker on a 10 mil clear PVC film (polyvinyl chloride film from Laird Plastics) with a #28 Mylar rod to prime a 1×1 inch area of 1 inch wide strips of the PVC films. Dry to touch and cut the primed PVC film into 1×2 inch strips. Heat seal the primed strip to another uncoated 1×2 inch PVC strip using a Sentinal Heat Sealer at 50 psi nip pressure with a 30 second dwell time. The sealing temperature (activation temperature) selected are 125, 150, 175 and 200° F. Allow the bonds to age 7 days and then measure the heat resistance temperature.
A 100 g weight was attached to each PVC bond in a T-peel configuration and then placed in the Tenney oven. The T-peels had a 1 square inch bond area. The T-peels were subjected to a 25° C. increase in temperature each hour until 125° C. The temperatures and the times were recorded by the Tenney sensing unit upon bond failure.
The following abbreviations are used in the Examples:
______________________________________
Rucoflex XS--55
a sulfonated polyester polyol based on
5-sulfoisophthalic acid monosodium salt,
adipic acid and 1,6-hexanediol, OH
number 49.0
DMPA dimethylolpropionic acid
1,4-BD 1,4-butanediol
TMXDI tetramethylxylyenediisocyanate
IPDI isophorone diisocyanate
HDI hexamethylenediisocyanate
EDA ethylenediamine
TEA triethylamine
NMP 1-methyl-2-pyrrolidone
DPMA cupropylene glycol methyl ether acetate
Desmodur DA dispersible polyisocyanate based on
HDI timer (Bayer)
CX-100 a 100% active polyfunctional aziridine
liquid crosslinker (ICI)
______________________________________
Example 1
Two component
Starting materials:
213.8 g of Rucoflex XS--55
13.4 g of DMPA
40.3 g of HDI
14.6 g of TMXDI
5.1 g of EDA
9.0 g of TEA
90 g of NMP
550.4 g of water
Preparation method:
The Rucoflex XS--55 was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C. The DMPA, TMXDI and HDI were added, whereupon the temperature was maintained at about 80° F. for 3 hours and then cooled to about 65°-70° C. At this temperature, the TEA was added and stirred for 10-15 minutes. The temperature was further reduced to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA. A finely divided dispersion having a solids content of 32.0% and a pH of 8.5 was obtained.
100.0 g of the aqueous polyurethane dispersion prepared above was mixed with 4.0 g of Desmodur DA (DDA) at room temperature to make a two component adhesive composition.
100.0 g of the same aqueous polyurethane dispersion was mixed with 2.0 g of CX-100, a commercial polyaziridine crosslinker compound, at room temperature to make another two component adhesive composition.
The heat resistance of the aqueous polyurethane dispersion, the two-component adhesive compositions were tested. The testing results are shown in Table 2.
Example 2
Two component formulations
Starting materials:
213.8 g of Rucoflex XS--55
6.7 g of DMPA
9.0 g of 1,4-BD
18.3 g of TMXDI
50.4 g of HDI
6.4 g of EDA
4.5 g of TEA
90.0 g of NMP
598.7 g of water
Preparation method:
The method for preparing the dispersion of Example 2 was the same as the method for Example 1 except that the 1,4-BD was added at the same time as the DMPA. A finely divided dispersion having a solids content of 31.4% and a pH of 7.95 was obtained.
Two different two-component adhesive compositions were prepared following the same method as in Example 1. The testing results for heat resistance are shown in Table 2.
Examples 3-5
Two-component formulations
Compositions were prepared as shown in Table 1.
TABLE 1
______________________________________
Starting materials for Examples 3-5
Starting materials (g)
Comparative
Example 3 Example 4 Example 5
______________________________________
-55 213.8 213.8 213.8
DMPA 6.7 13.4 13.4
1,4-BD 4.5 0.0 22.5
IPDI 22.2 22.2 49.95
HDI 33.6 33.6 75.6
EDA 5.1 5.1 11.5
TEA 4.5 9.0 9.0
NMP 90.0 90.0 90.0
Water 570.6 580.7 728.6
Dispersion Properties
Solids 31.5 31.6 32.6
content
pH 7.5 8.0 8.1
______________________________________
The preparation method for Examples 3-5 was the same as the method of Examples 1-2 except that IPDI was used instead of TMXDI.
The testing results for heat resistance are shown in Table 2, where PUD refers to the one component dispersion, PUD/DDA to its mixture with Desmondur DA crosslinker and PUD/CX100 to its mixture with CX-100 polyfunctional aziridine crosslinker.
TABLE 2
______________________________________
Heat Resistance Temperature (°F.) of Examples 1-5
Activation Temp. (°F.)
125 150 175 200
______________________________________
Example 1
PUD RT 191 196 199
PUD/DDA 129 236 240 242
PUD/CX100 237 NF, 1/2" NF, 1/2"
NF, 1/2"
peeled peeled peeled
Example 2
PUD 229 228 223 225
PUD/DDA 231 235 238 243
PUD/CX100 NF, 7/8" NF, 15/16"
NF, 7/8"
243
peeled peeled peeled
Example 3
PUD 226 222 227 230
PUD/DDA 238 238 241 243
PUD/CX100 NF, 3/4" NF, 3/4" NF, 7/8"
NF, 15/16"
peeled peeled peeled peeled
Example 4 (comparative example)
PUD 218 219 218 226
PUD/DDA 241 238 238 240
PUD/CX100 241 246 NF, 15/16"
NF, 3/4"
peeled peeled
Example 5
PUD RT 75 84 211
PUD/DDA 229 242 245 NF, 15/16"
peeled
PUD/CX100 NF, 3/4" NF, 3/4" NF, 3/4"
NF, 7/8"
peeled peeled peeled peeled
______________________________________
RT: room temperature
NF: no failure until 260° F. Where bond had begun to peel at
260° F. the extent of peeling is indicated.
Example 6
One-component formulation
Starting materials:
213.8 g of Rucoflex XS--55
6.7 g of DMPA
13.5 g of 1,4-BD
21.96 g of TMXDI
60.48 g of HDI
7.65 g of EDA
4.5 g of TEA
90.0 g of NMP
627.9 g of water
Preparation method:
The Rucoflex XS--55 was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C. The DMPA, 1,4-BD, TMXDI and HDI were added, whereupon the temperature was maintained at about 80° C. for 3 hours and then cooled to 65°-70° C. At this temperature, the TEA was added and stirred for 10-15 minutes. The temperature was further cooled to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA.
A finely divided dispersion having a solids content of 31.4% and a pH of 7.3 was obtained. This dispersion had good water resistance and high heat resistance and could be used as a one-component adhesive.
The test results for heat resistance of the dispersion are shown in Table 4.
Examples 7-14
One-component formulations
TABLE 3
__________________________________________________________________________
Starting materials for Examples 7-12
Starting
Example
Example
Example
Example
Example
Example
Example
Example
materials
7 8 9 10 11 12 13 14
__________________________________________________________________________
Rucoflex
213.8
213.8
213.8
213.8
213.8
213.8
213.8
213.8
XS--
55
DMPA 13.4 13.4 13.4 13.4 6.7 6.7 6.7 6.7
1,4-BD
13.5 4.5 9.0 13.5 9.0 13.5 9.0 9.0
TMXDI
25.62
0 0 0 0 0 0 0
IPDI 0 27.75
33.3 38.85
27.75
33.3 27.75
27.75
HDI 70.56
42.0 50.4 58.8 42.0 50.4 42.0 42.0
EDA 8.93 6.38 7.65 8.93 6.38 7.65 6.38 5.63
TEA 9.0 9.0 9.0 9.0 4.5 4.5 4.0 4.0
Acetone
0 0 0 0 0 0 50.0 50.0
NMP 90.0 90.0 90.0 90.0 90.0 90.0 0 0
Water
667.2
610.2
639.8
669.4
600.2
629.8
558.0
574.5
__________________________________________________________________________
Preparation method:
The dispersion preparation method Examples 7-14 was the same as the method of Example 6 except for the use of IPDI instead of TMXDI in Examples 8-14 and the use of acetone solvent in Examples 13-14 in place of NMP solvent. The testing results of the heat resistance are shown in Table 4.
All of the dispersion prepared in Examples 7-14 have good water resistance and high heat resistance and can be used as one-component adhesives.
TABLE 4
______________________________________
Heat resistance temperature (°F.) of Examples 6-12
Activation temp. (°F.)
125 150 175 200
______________________________________
Example 6
<100 206 NF, 3/4"
NF, 1/2"
peeled peeled
Example 7
236 NF, 7/8" NF, 3/4"
NF, 3/4"
peeled peeled peeled
Example 8
NF, 15/16"
NF, 15/16"
225 NF, 15/16"
peeled peeled peeled
Example 9
NF, 1/2" NF, 1/4" NF, 1/16"
NF, 1/16"
peeled peeled peeled peeled
Example 10
NF, 1/4" NF, 1/4" NF, 1/32"
NF, 1/32"
peeled peeled peeled peeled
Example 11
NF, 1/8" NF, 1/8" NF, 3/16"
NF, 1/4"
peeled peeled peeled peeled
Example 12
NF, 1/16" NF, 1/16" NF, 1/8"
NF, 1/16"
peeled peeled peeled peeled
Example 13
NF NF NF NF
Example 14
NF NF NF NF
______________________________________
NF: no failure until 260° F.
Example 15 (Comparative Example)
In this example, formulations of Disperecoll KA , an aqueous polyurethane dispersion product of Bayer Corporation, based on HDI and IPDI (Formulation B), and of an embodiment of the sulfonated polyester containing polyurethane dispersion invention of copending application Ser. No. 08/126,508, filed Sep. 24, (Formulation A), were prepared and tested for heat resistance in one component and two-component compositions, the second component being a commercial polyisocyanate crosslinker. The crosslinker employed was Desmodur DA (Bayer, a dispersible polyisocyanate based on trimer of hexamethylenediisocyanate). The sulfonated polyester containing polyurethane dispersion, Formulation A, was prepared from the following ingredients:
5.0% Rucofiex XS--55(sulfonated polyester polyol based on 5 sulfoisophthalic acid monosodium salt, adipic acid and 1,6-hexanediol, OH number 49.0)
3.4% hexamethylene diisocyanate (HDI)
1.2% tetramethylxylylene diisocyanate (TMXDI)
0.4% ethylenediamine (EDA)
60.0% water
Heat resistance was determined as in the previous examples.
TABLE 5
______________________________________
Heat resistance (°F.)
Activation temp. (°F.)
Formulation
125 150 175 200
______________________________________
A 221 227 225 233
A + 5% 219 236 244 238
Desmodur DA
B 199 220 221 223
B + 5% 247 NF to /2"
NF to 260
NF to 260
Desmodur DA peeled
______________________________________
*PVC as substrate
NF = No failure until 260° F.
Comparison of the results shown in Tables 4 and 5 demonstrate that the use of the compositions of the invention as one-component adhesives provides adhesive bonds which are comparable in strength to prior art two-component crosslinked PUD formulations.
Example 16
Films made from the one-component aqueous polyurethane dispersions of Examples 8-14 were immersed in water for 7 days, after which they had not changed. Films made from KA- in Example 15 (uncrosslinked), by contrast, had totally lost their strength after immersing in water for only 1 day.
Examples 17-18
______________________________________
Starting materials:
Example 17
Example 18
______________________________________
Rucoflex XS--55
213.8 g 213.8 g
DNDA 6.7 g 13.4 g
1,4-BD 4.5 g 22.5 g
IPDI 66.6 g 149.9 g
Dibutyltin dilaurate
2 drops 3 drops
EDA 3.83 g 11.5 g
TEA 4.0 g 9.0 g
NMP 88.3 g 123.3 g
water 588.3 g 821.5 g
______________________________________
Preparation method:
The Rucoflex XS--55 was dried in vacuo at 100° C. and then dissolved into the NMP at 70°-80° C. The DMPA, 1,4-BD, and IPDI were added, whereupon the temperature was maintained at about 85° C. for 3 hours and then cooled to 65°-70° C. At this temperature, the TEA was added and stirred for 10-13 minutes. The temperature was further cooled to about 60° C., the prepolymer was dispersed by adding the water and extended by adding the EDA.
______________________________________
Properties: Example 17
Example 18
______________________________________
Solids (%) 31.1 30.9
pH 9.5 9.8
Particle size (nm)
126 101
Viscosity (cps) 250 400
______________________________________
Crosslinkers used were 5% by weight Desmondur DA and 2% by weight CX-100. Heat resistance was determined as in the previous examples. Results are shown in Table 6.
TABLE 6
______________________________________
Heat Resistance Temperature (°F.) of Examples 17-18
Activation Temp. (°F.)
125 150 175 200
______________________________________
Example 17
PUD 137 189 193 194
PUD/DDA NF, 1/3" NF, 2/3" NF, 1/2"
NF, 1/4"
peeled peeled peeled peeled
PUD/CX100
NF, 1/3" 248 NF, 7/8"
NF, 3/4"
peeled peeled peeled
Example 18
PUD RT RT RT 90
PUD/DDA 232 236 243 243
PUD/CX100
NF, 2/3" NF, 2/3" NF, 1/2"
NF, 1/2"
peeled peeled peeled peeled
______________________________________
Claims (28)
What is claimed is:
1. An aqueous dispersion of an anionic polyurethane, the polyurethane comprising the reaction product of an isocyanate terminated polyurethane prepolymer, and an amine functional chain extender, the polyurethane prepolymer comprising the reaction product of a polyol component and a diisocyanate component, the polyol component comprising:a sulfonated polyester polyol, a hydroxy carboxylic acid of the formula:
(HO).sub.x R(COOH).sub.y
wherein (R) represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, and a low molecular weight aliphatic diol having a number average molecular weight of from 60 to 400.
2. A dispersion as in claim 1 wherein the low molecular weight aliphatic diol is a C2 -C8 alkylene diol.
3. A dispersion as in claim 2 wherein the low molecular weight aliphatic diol is ethylene glycol, 1,3-propylene glycol, 1,4-butanediol or 1,6-hexanediol.
4. A dispersion as in claim 1 wherein the sulfonated polyester polyol is a hydroxy terminated polyester formed of residues from at least one carboxylic diacid, at least one diol and at least one sulfonate diacid or sulfonate diol.
5. A dispersion as in claim 4 wherein the carboxylic diacid residue of the sulfonated polyester polyol comprises the residue of a diacid selected from the group consisting of adipic, azelaic, succinic, suberic and phthalic acids.
6. A dispersion as in claim 4 wherein the diol residue of the sulfonated polyester polyol comprises the residue of a diol selected from the group consisting of ethylene glycol, condensates of ethylene glycols, butanediol, butenediol, propanediol, neopentyl glycol, hexanediol, 1,4-cyclohexane dimethanol, 1,2-propylene glycol and 2-methyl- 1,3-propanediol.
7. A dispersion as in claim 4 wherein the sulfonate diacid or sulfonate diol residue comprises the residue of at least one member of the group consisting of sulfoisophthalic acid, sulfosuccinic acid, 1,4-dihydroxybutane sulfonic acid and succinaldehyde disodium bisulfite.
8. A dispersion as in claim 1 wherein the sulfonated polyester polyol is based on 5-sulfoisophthalic acid monosodium salt, 1,6-hexanediol and adipic acid.
9. A dispersion as in claim 1 wherein the sulfonated polyester polyol has a number average molecular weight in the range of about 500 to 10,000 and a melting temperature in the range of about 10° to 100° C.
10. A dispersion as in claim 9 wherein the number average molecular weight range is about 1,000 to 4,000 and the melting temperature is about 40° to 60° C.
11. A dispersion as in claim 10 wherein the polyisocyanate is a mixture of hexamethylenediisocyanate (HDI) and one of tetramethylxylylenediisocyanate (TMXDI) and isophoronediisocyanate (IPDI).
12. A dispersion as in claim 11 wherein the polyisocyanate is a mixture of HDI and IPDI, the hydroxycarboxylic acid is 2,2-dimethylolpropionic acid (DMPA) and the low molecular weight aliphatic diol is 1,4-butanediol.
13. A dispersion as in claim 12 wherein the polyurethane prepolymer is the reaction product of said polyol and polyisocyanate components in the following weight ratios, based on 100 parts by weight of said polyol and polyisocyanate:Sulfonated polyester polyol from about 63.2 to about 71.5 DMPA from about 2.1 to about 4.4 1,4-butanediol from about 1.5 to about 4.2 IPDI from about 9.1 to about 11.5 HDI from about 13.9 to about 15.9.
14. A dispersion as in claim 1 wherein the hydroxy carboxylic acid is a α,α-dimethylol alkanoic acid represented by the formula: ##STR2## where R1 denotes hydrogen or an alkyl group with up to 9 carbon atoms.
15. A dispersion as in claim 14 wherein the α,α-dimethylol alkanoic acid is selected from the group consisting of 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanic acid and mixtures thereof.
16. A dispersion as in claim 15 wherein the α,α-dimethylol alkanoic acid is 2,2-dimethylolpropionic acid.
17. An adhesive formulation prepared by blending a dispersion as in claim 1 with an acid reactive crosslinking agent.
18. An adhesive formulation as in claim 17 wherein the crosslinking agent is selected from the group consisting of polyfunctional aziridines, zinc ammonium carbonate and zirconium carbonate.
19. An adhesive as in claim 17 wherein the crosslinking agent is a polyfunctional aziridine, the adhesive having a heat resistance temperature of at least 260° F., said heat resistance temperature being the temperature at which a 100 gm load is dropped, said load being attached in T-peel configuration on a 1 inch by 1 inch laminate of PVC films prepared by applying the adhesive to one of said films, drying the adhesive, applying the second of said films at an activation temperature of no more than 150° F. and then aging the laminate for 7 days.
20. An adhesive formulation prepared by blending a dispersion as in claim 1 with a polyisocyanate crosslinking agent.
21. A bonded assembly of a pair of substrates, the assembly bonded with an adhesive comprising a dried dispersion of claim 1.
22. A bonded assembly as in claim 21 wherein, the substrate pairs include a member made of a material selected from the group consisting of polypropylene, polyvinyl chloride, phenolic composite, leather, styrene-butadiene rubber, fiberboard, paper, polyvinyl fluoride, wood, wood composite, recycled wood, polyethylene terephthalate, polyethylene, and metal.
23. A bonded assembly as in claim 21 wherein said dispersion consists essentially of said polyurethane.
24. A bonded assembly as in claim 21 wherein said dispersion further comprises at least one of an acrylic, an epoxy, a vinyl, or a second polyurethane polymer.
25. A bonded assembly as in claim 21 wherein said adhesive further comprises a polyisocyanate or acid reactive crosslinker.
26. A bonded assembly as in claim 21 wherein said substrate pair is selected from the group consisting of polypropylene foam/polyvinyl chloride; polyvinyl fluoride/phenolic composite; leather/styrene-butadiene rubber; PVC/fiberboard; paper/paper; polyvinyl fluoride/polyvinyl chloride; polyvinyl fluoride/wood; polyvinyl fluoride/wood composite; polyvinyl fluoride/recycled wood; polyvinyl fluoride/paper products; polyethylene terephthalate/polypropylene; polyethylene terephthalate/polyethylene; polyethylene terephthalate/metal and plasticized polyvinyl chloride/plasticized polyvinyl chloride.
27. An adhesive formulation prepared by blending a dispersion as in claim 1 with at least one of an acrylic, an epoxy, a vinyl, or a second polyurethane polymer.
28. A dispersion as in claim 1 having a heat resistance temperature of at least 260° F., said heat resistance temperature being the temperature at which a 100 gm load is dropped, said load being attached in T-peel configuration on a 1 inch by 1 inch laminate of PVC films prepared by applying the dispersion, without any added crosslinker, to one of said films, drying the dispersion, applying the second of said films at an activation temperature of no more than 200° F. and then aging the laminate for 7 days.
US08/304,653
-09-24
-09-09
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
Expired - Fee Related
USA
(
en)
Priority Applications (16)
Application Number
Priority Date
Filing Date
Title
US08/304,653
USA
(
en)
-09-24
-09-09
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
US08/343,676
USA
(
en)
-09-24
-11-22
Aqueous anionic poly (urethane/urea) dispersions
NZA
NZA
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive; bonded assemblies
AU/95A
AUB2
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
JPA
JPB2
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive composition with improved heat resistance
KRA
KRB1
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
PCT/US/
WOA1
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
EPA
EPB1
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
CAA
CAA1
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
MXA
MXA
(
en)
-09-09
-01-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance.
ATT
ATET1
(
en)
-09-09
-01-04
AQUEOUS POLYURETHANE DISPERSION ADHESIVE COMPOSITIONS WITH IMPROVED HEAT RESISTANCE
EST
EST3
(
en)
-09-09
-01-04
ADHESIVE COMPOSITIONS OF AQUEOUS POLYURETHANE DISPERSION WITH OPTIMIZED HEAT RESISTANCE.
DET
DET2
(
en)
-09-09
-01-04
AQUEOUS POLYURETHANE DISPERSION ADHESIVE COMPOSITIONS WITH IMPROVED HEAT RESISTANCE
US08/480,780
USA
(
en)
-09-24
-06-07
Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
US08/528,936
USA
(
en)
-09-09
-09-15
Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance
US08/561,197
USA
(
en)
-09-09
-11-21
Water-based polyurethanes for footwear
Applications Claiming Priority (2)
Application Number
Priority Date
Filing Date
Title
USA
-09-24
-09-24
US08/304,653
USA
(
en)
-09-24
-09-09
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
Related Parent Applications (1)
Application Number
Title
Priority Date
Filing Date
USA
Continuation-In-Part
-09-24
-09-24
Related Child Applications (4)
Application Number
Title
Priority Date
Filing Date
US08/343,676
Continuation-In-Part
USA
(
en)
-09-24
-11-22
Aqueous anionic poly (urethane/urea) dispersions
US08/480,780
Continuation-In-Part
USA
(
en)
-09-24
-06-07
Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
US08/528,936
Continuation-In-Part
USA
(
en)
-09-09
-09-15
Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance
US08/561,197
Continuation-In-Part
USA
(
en)
-09-09
-11-21
Water-based polyurethanes for footwear
Publications (1)
Publication Number
Publication Date
USA
true
USA
(
en)
-03-04
Family
ID=
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
US08/304,653
Expired - Fee Related
USA
(
en)
-09-24
-09-09
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
Country Status (12)
Country
Link
US
(
1)
USA
(
en)
EP
(
1)
EPB1
(
en)
JP
(
1)
JPB2
(
en)
KR
(
1)
KRB1
(
en)
AT
(
1)
ATET1
(
en)
AU
(
1)
AUB2
(
en)
CA
(
1)
CAA1
(
en)
DE
(
1)
DET2
(
en)
ES
(
1)
EST3
(
en)
MX
(
1)
MXA
(
en)
NZ
(
1)
NZA
(
en)
WO
(
1)
WOA1
(
en)
Cited By (76)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
USA
(
en)
*
-09-24
-12-30
H.B. Fuller Licensing & Financing, Inc.
Aqueous anionic poly (urethane/urea) dispersions
USA
(
en)
*
-07-31
-06-09
Nippon Paint Co., Ltd.
Urethane prepolymer, process for producing urethane prepolymer, isocyanate compound, and polyurethane dispersion
USA
(
en)
*
-08-13
-09-15
H.B. Fuller Licensing & Financing, Inc.
Water-based sulfonated polymer compositions
USA
(
en)
*
-09-09
-02-16
H. B. Fuller Licensing & Financing, Inc.
Water-based polyurethanes for footwear
USA
(
en)
*
-03-05
-05-04
H.B. Fuller Licensing & Financing, Inc.
Aqueous polyurethane dispersions formed from polyisocyanates having a methylene bridge
EPA1
(
en)
*
-04-30
-11-03
Morton International, Inc.
Heat-activatable polyurethane/urea adhesive in aqueous dispersion
USA
(
en)
*
-06-17
-01-25
H.B. Fuller Licensing & Financing,Inc.
Stable aqueous polyurethane dispersions
USA
(
en)
*
-12-18
-12-26
Witco Corporation
Polyurethane synthesis from functional group terminated polymers containing sulfonate groups
USB1
(
en)
*
-01-30
-03-27
Rextrude Co.
Precemented welt
USB1
(
en)
-06-04
-05-22
H. B. Fuller Licensing & Financing, Inc.
Aqueous laminating adhesive composition and a method of using thereof
USB1
(
en)
*
-02-09
-05-29
Surface Solutions Laboratories, Inc.
Articles prepared from water-based hydrophilic coating compositions
USB1
(
en)
*
-06-04
-06-19
H. B. Fuller Licensing & Financing, Inc.
Dry bond film laminate employing acrylic emulsion adhesives with improved crosslinker
USB1
(
en)
-12-29
-08-07
The Dow Chemical Company
Polyurethane foams prepared from mechanically frothed polyurethane dispersions
USB1
(
en)
-12-08
-09-11
H. B. Fuller Licensing & Financing, Inc.
Process for improving hydrolysis resistance of polyurethane dispersion adhesives and bonded assemblies produced therefrom
USB1
(
en)
-04-05
-10-23
3M Innovative Properties Company
Low temperature thermally activated water-dispersed adhesives
USB1
(
en)
-04-05
-10-30
3M Innovative Properties Company
Water-dispersed adhesive compositions
USB1
(
en)
-03-17
-02-19
Ameritherm, Inc.
RF active compositions for use in adhesion, bonding and coating
USB1
(
en)
-04-05
-09-03
3M Innovative Properties Company
Water-dispersed polymer stabilizer
USB2
(
en)
-09-21
-02-04
Cytec Technology Corp.
Low-temperature, heat-activated adhesives with high heat resistance properties
USB1
(
en)
-02-25
-02-11
3M Innovative Properties Co.
Polyurethane-based pressure-sensitive adhesives, systems for such adhesives, articles therefrom, and methods of making
USB1
(
en)
-04-05
-04-01
3M Innovative Properties Company
Low temperature thermally activated water-dispersed adhesive compositions
USA1
(
en)
*
-11-02
-05-08
Chunbin Zhang
Primer composition for promoting adhesion of a urethane adhesive to a polymeric substrate
USB2
(
en)
*
-11-30
-06-24
Bayer Corporation
Stable isocyanate formulations
USA1
(
en)
*
-08-02
-07-10
3M Innovative Properties Company
Al2O3-rare earth oxide-ZrO2/HfO2 materials, and methods of making and using the same
WOA1
(
en)
*
-01-18
-07-24
Youlu Duan
Aqueous polyurethane dispersions used as adhesives and coatings and its preparation
USB1
(
en)
-02-25
-11-04
3M Innovative Properties Company
Polyurethane-based adhesives, systems for such adhesives, articles therefrom, and methods of making
USB2
(
en)
-09-23
-11-18
Codaco, Inc.
Radio frequency (RF) heating system
USB2
(
en)
*
-03-23
-03-30
Ashland Inc.
Peelable foam coating composition
USA1
(
en)
*
-03-23
-02-03
Zhiqiang Zhang
Peelable coating composition
USA1
(
en)
*
-12-19
-06-23
3M Innovative Properties Company
Polyurethane-based pressure sensitive adhesives and methods of manufacture
USA1
(
en)
*
-01-12
-07-14
Minyu Li
Jobsite-renewable multilayer floor finish with enhanced hardening rate
WOA1
(
en)
*
-04-13
-10-27
Lamberti S.P.A.
Adhesive aqueous compositions
USA1
(
en)
*
-12-23
-06-29
Rearick Brian K
Coated compressible substrates
USA1
(
en)
*
-12-23
-06-29
Rearick Brian K
Color harmonization coatings for articles of manufacture comprising different substrate materials
USA1
(
en)
*
-04-08
-10-12
Ilmenev Pavel E
Method for preparing polyurethane dispersions
USA1
(
en)
*
-05-28
-11-23
Lonza Inc.
Quaternary ammonium salts containing non-halogen anions as anticorrosive agents
USA1
(
en)
*
-12-23
-01-25
Trainham James A
Flexible polymer coating and coated flexible substrates
USA1
(
en)
*
-08-13
-02-01
Valspar Sourcing, Inc.
Water-based polyurethane-polyethylene compositions
EPA1
(
en)
*
-11-26
-05-30
Bayer MaterialScience AG
Aqueous dispersions of hydroxy-functional polyester containing urethane groups
WOA1
(
en)
-01-16
-07-19
Bwe I Malmö Ab
Low protonation constant hydroxy acids
USA1
(
en)
*
-09-22
-03-27
Steven Michael Baxter
Polymer compositions containing polyurethanes
USA1
(
en)
*
-09-17
-07-24
Ppg Industries Ohio, Inc.
Substrates and articles of manufacture coated with a waterborne 2k coating composition
USA1
(
en)
*
-03-27
-10-01
Ppg Industries Ohio, Inc.
Polycarbodiimides
CNB
(
en)
*
-11-01
-11-03
'''''''''''''
Polyurethane prepolymer, aquosity polyurethane binder and uses thereof
USA1
(
en)
*
-09-25
-03-31
Mcgee John D
Water-based adhesive for lamination of polymers to metal substrates
CNB
(
en)
*
-02-10
-11-30
''''''''''
Method of preparing polyurethane resin for new shoe leather
CNA
(
en)
*
-10-29
-07-11
''''''''''
Aqueous formulations based on crystalline or semi-crystalline polyurethane polymers
CNA
(
en)
*
-05-23
-09-25
''''''''''
Production method of waterborne polyurethane used for artificial leather bonding resin
USA1
(
en)
*
-09-22
-05-15
Lintec Corporation
Flame retardant adhesive sheet
USB2
(
en)
-04-09
-06-03
Bayer Materialscience Llc
Two-component waterborne polyurethane coatings
USB2
(
en)
-02-18
-02-10
Eastern Michigan University
Bio-based polyurethane dispersion compositions and methods
USB2
(
en)
-05-03
-07-14
Surface Solutions Laboratories
Coating resins and coating with multiple crosslink functionalities
WOA1
(
en)
-10-29
-05-06
Resinate Materials Group, Inc.
High recycle content polyester polyols from hydroxy-functional ketal acids, esters or amides
WOA1
(
en)
*
-01-21
-07-28
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
CNA
(
en)
*
-07-05
-09-07
''''''
Biomass-resource-modified water-based polyurethane emulsion and preparation method thereof
WOA1
(
en)
*
-03-12
-09-15
Henkel Ag & Co. Kgaa
Aqueous polyurethane dispersions
WOA1
(
en)
-03-20
-09-29
Resinate Materials Group, Inc.
Cycloaliphatic polyester polyols from thermoplastic polyesters
USB2
(
en)
-01-21
-11-01
Resinate Materials Group, Inc.
High recycle content polyols from thermoplastic polyesters and lignin or tannin
USB2
(
en)
-03-20
-12-20
Resinate Materials Group, Inc.
Cycloaliphatic polyester polyols from thermoplastic polyesters
WOA1
(
en)
*
-09-21
-03-30
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
JPWOA1
(
en)
*
-06-20
-05-25
''''''''
Aqueous polyurethane resin dispersion
USB2
(
en)
-01-30
-07-25
Resinate Materials Group, Inc.
Integrated process for treating recycled PET and PTT materials
USB2
(
en)
-05-05
-12-12
Resinate Materials Group, Inc.
Polyester polyols from thermoplastic polyesters and dimer fatty acids
USB2
(
en)
-12-15
-04-17
H.B. Fuller Company
Reactive film adhesives with enhanced adhesion to metallic surfaces
USB2
(
en)
*
-12-03
-05-15
Rohm And Haas Company
Aqueous polyurethane dispsersions
WOA1
(
en)
-03-03
-09-07
Resinate Materials Group, Inc.
Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom
USA1
(
en)
*
-10-11
-04-11
Eastman Kodak Company
Method of inkjet printing
WOA1
(
en)
-12-21
-06-27
Covestro Deutschland Ag
Frost-resistant adhesives based on polyisocyanates
USB2
(
en)
-08-20
-09-17
Resinate Materials Group, Inc.
High recycle content polyester polyols
USB2
(
en)
-04-14
-03-02
Resinate Materials Group, Inc.
Polyester polyols with increased clarity
CNA
(
en)
*
-01-11
-05-28
''''''''''''''
High-temperature-resistant water polyurethane, preparation method thereof, water-based polyurethane adhesive and preparation method thereof
CNA
(
en)
*
-12-20
-04-22
''''
Sizing agent for preventing Lycra cotton yarn from bonding and sizing process thereof
USB2
(
en)
-02-28
-04-18
3M Innovative Properties Company
Polyurethane adhesive with chemical resistant
USB2
(
en)
-11-19
-08-22
Covestro Llc
Polyisocyanate resins
USB2
(
en)
-07-30
-10-31
H.B. Fuller Company
Polyurethane adhesive film
USB2
(
en)
-05-04
-12-19
Carlisle Construction Materials, LLC
Polyurethane dispersions and their use to produce coatings and adhesives
Families Citing this family (21)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
USA
(
en)
*
-09-09
-06-10
H.B. Fuller Licensing And Financing, Inc.
Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance
AUB2
(
en)
*
-09-09
-11-18
H.B. Fuller Licensing And Financing Inc.
Improved water-based polyurethanes for footwear
CAA1
(
en)
*
-06-07
-12-19
H.B. Fuller Licensing & Financing, Inc.
Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
USA
(
en)
*
-08-31
-05-12
National Starch And Chemical Investment Holding Corporation
Hot melt adhesives based on sulfonated polyesters
USA
(
en)
*
-09-16
-02-10
H. B. Fuller Licensing & Financing, Inc.
Melamine-formaldehyde resin based adhesive compositions
USB1
(
en)
-02-17
-01-30
3M Innovative Properties Company
Waterbased thermoforming adhesives
ATET1
(
en)
-12-24
-04-15
Akzo Nobel Nv
AQUEOUS COATING COMPOSITION AND A POLYOL FOR SUCH A COMPOSITION
USB1
(
en)
-04-09
-06-25
National Starch And Chemical Investment Holding Corporation
Use of high hydroxyl compounds for water sensitive hot melt adhesives
USA
(
en)
*
-04-09
-12-14
National Starch And Chemical Investment Holding Corporation
Use of anionic or cationic plasticizers with sulfonated polyesters in hot melt formulations
USB1
(
en)
-04-09
-11-25
National Starch And Chemical Investment Holding Corporation
Hot melt adhesives based on sulfonated polyesters comprising wetness indicator
EPA3
(
en)
*
-12-21
-05-08
Alfa Klebstoffe Ag
Adhesive bond
JPB2
(
en)
-07-19
-06-25
'''''''
Aqueous polyurethane resin dispersion and aqueous adhesive
KRB1
(
en)
-07-10
-04-01
'''''''''''
Polyurethane adhesives for packaging and method for preparing the same
JPB2
(
en)
*
-07-22
-03-16
''''''''
Urethane emulsion and aqueous polyurethane composition using the same
EPA1
(
en)
*
-11-14
-05-19
Bayer MaterialScience AG
Networkable polyurethane dispersions
CNB
(
en)
*
-12-30
-01-12
''''''
Polyvinyl chloride plastisol and preparation method thereof
EPB1
(
en)
*
-07-29
-04-10
Basf Se
Biologically disintegratable composite films
KRB1
(
en)
-03-19
-05-27
'''' ''''
Primer for industry rubber
JPWOA1
(
en)
*
-12-05
-01-05
'''''''
Copolymer polyurethane resin and water-based emulsion
JPB1
(
en)
*
-04-14
-01-18
''''''''''
Method for producing polyimide aqueous dispersion
WOA1
(
en)
*
-04-14
-10-19
''''''''''
Aqueous polyimide dispersion, binder for electrodes, electrode, secondary battery and method for producing aqueous polyimide dispersion
Citations (73)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
USA
(
en)
*
-10-14
-02-16
Dynamit Nobel Ag
Process for the polymerization of vinyl chloride with a catalyst mixture of trialkyl aluminum and boric acid trialkyl ester and a cocatalyst
DEB
(
en)
*
-01-16
-09-09
Bayer Ag
Process for the preparation of N- (omega-aminoalkyl) -aminoalkanesulfonic acids
BEA
(
en)
*
-12-08
-04-01
FRA
(
en)
*
-02-13
-07-01
Goodyear Tire & Rubber
New polyurethane compositions and their preparation process
CAA
(
en)
*
-07-25
Keberle Wolfgang
Polyurethane plastics
GBA
(
en)
*
-10-16
-09-25
Bayer Ag
Polyurethane compositions
USA
(
en)
*
-09-19
-11-18
Bayer Ag
Polyurethane plastics
CHA
(
en)
*
-11-24
-12-15
Merck & Co Inc
Process for the production of a polyurethane which gives a clear solution at 25o C with at least the same volume of heavy gasoline
USA
(
en)
*
-10-23
-12-05
Bayer Ag
Process for the production of modified anionic emulsion polymers with anionic polyurethane
CAA
(
en)
*
-07-18
-06-12
Keberle Wolfgang
N-(w-aminoalkane)-w'-aminoalkane sulphonic acid salts and their use as anionic structural components in the preparation of emulsifier/free polyurethane dispersions
USA
(
en)
*
-10-16
-08-27
Ppg Industries Inc
Lactone reaction products
USA
(
en)
*
-11-24
-02-18
American Cyanamid Co
Adhesive color printing system for floor coverings and other home furnishings fabrics
USA
(
en)
*
-04-29
-03-11
Bayer Ag
Preparation of cross-linked particles of polyurethane or polyurea containing ionic groups
USA
(
en)
*
-08-29
-11-11
Ppg Industries Inc
Composition useful in making extensible films
DEA1
(
en)
*
-08-02
-02-26
Bayer Ag
DIHYDROXYSULFONATES CONTAINING AETHER STRUCTURES
DEA1
(
en)
*
-09-28
-04-08
Bayer Ag
PROCESS FOR THE PRODUCTION OF POLYURETHANES
USA
(
en)
*
-06-02
-01-03
Ppg Industries, Inc.
Water-reduced urethane coating compositions
USA
(
en)
*
-11-14
-05-30
Bayer Aktiengesellschaft
Production of water-dispersible polyurethanes having ionic groups and hydrophilic side chains
USA
(
en)
*
-05-26
-07-04
Ppg Industries, Inc.
Polylactone-polyurethanes and aqueous dispersions thereof
USA
(
en)
*
-09-28
-08-22
Bayer Aktiengesellschaft
Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols
USA
(
en)
*
-10-12
-08-29
Rhone-Progil
Polyurethane latexes from sulfonate prepolymer, aqueous chain extension process, and coated support
USA
(
en)
*
-06-02
-04-03
Ppg Industries, Inc.
Water-reduced urethane coating compositions
USA
(
en)
*
-12-10
-02-26
Bayer Aktiengesellschaft
Water-dispersible polyurethanes
USA
(
en)
*
-10-04
-05-20
Textron, Inc.
Aqueous colloidal dispersions of tertiary amine salts of urea-urethane polymers and method for manufacture
USA
(
en)
*
-11-11
-12-02
Bayer Aktiengesellschaft
Process for the preparation of polyurethanes which are dispersible in water
USA
(
en)
*
-10-15
-03-03
Ricoh Company, Ltd.
Pressure sensitive adhesive toner of clustered encapsulated porous particles for use in electrostatic photography
USA
(
en)
*
-03-29
-07-07
Textron, Inc.
Water-dispersible urethane polymers and aqueous polymer dispersions
USA
(
en)
*
-04-18
-12-01
Bayer Aktiengesellschaft
Polyurethanes which are dispersible or soluble in water and a process for their preparation
USA
(
en)
*
-04-30
-12-22
Minnesota Mining And Manufacturing Company
Aqueous solvent dispersible linear polyurethane resins
USA
(
en)
*
-12-19
-05-24
Bayer Aktiengesellschaft
Dispersions of polymers containing sulphonate groups, a process for the production thereof and their use as coating agents
USA
(
en)
*
-03-16
-07-17
Olin Corporation
Preparation of carboxylic acid-containing polyurethane prepolymers and aqueous dispersions thereof
USA
(
en)
*
-06-20
-02-26
Mobay Chemical Corporation
Stable, aqueous dispersions of polyurethane-ureas
USA
(
en)
*
-04-20
-09-10
Textron, Inc.
Water dispersible polyurethane adhesive compositions and adhesive layer formed therefrom
USA
(
en)
*
-01-19
-03-04
Bayer Aktiengesellschaft
Process for the production of polyurethanes, polyurethanes containing terminal aromatic amino groups and their use
USA
(
en)
*
-12-13
-03-18
Desoto, Inc.
Aqueous water-repellent coatings
USA
(
en)
*
-03-16
-05-20
Olin Corporation
Preparation of ionomers and polyurethane elastomers from carboxylic acid-containing monoether and polyether polyol addition products
USA
(
en)
*
-12-06
-11-18
Saint-Gobain Vitrage
Adhesive in preparation of laminates
USA
(
en)
*
-03-29
-01-13
Rohm And Haas Company
Process for preparing modified polymer emulsion adhesives
USA
(
en)
*
-04-18
-05-05
E. R. Squibb & Sons, Inc.
7-oxabicycloheptane substituted amides useful in the treatment of thrombotic disease
EPA2
(
en)
*
-11-14
-05-20
Bayer Ag
Process for the immobilization of biological material, particulate coagulates containing an immobilized biological material and their use as catalysts
EPA1
(
en)
*
-03-18
-09-23
Takeda Chemical Industries, Ltd.
Thermosetting resins and electrodeposition coating compositions containing the same
USA
(
en)
*
-09-16
-12-08
Vianova Kunstharz, A.G.
Self-crosslinking cationic paint binders containing urea and urethane groups and process of manufacture
USA
(
en)
*
-05-05
-08-09
Uniroyal Plastics Co., Inc.
Water-based thermoforming adhesives
USA
(
en)
*
-12-04
-08-16
Bayer Aktiengesellschaft
Water soluble or dispersible polyurethanes, a process for their preparation and their use for coating substrates
USA
(
en)
*
-04-15
-12-13
Basf Corporation, Inmont Division
Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics
EPA2
(
en)
*
-06-16
-12-21
W.R. Grace & Co.-Conn.
Crosslinked polyurethane emulsion, process and prepolymer for its production and process for forming coatings from said emulsion
USA
(
en)
*
-10-04
-01-31
Polyvinyl Chemicals Inc.
Coating compositions
EPA1
(
en)
*
-11-10
-05-17
BASF Lacke + Farben AG
Process for the preparation of macromonomers and macromonomers obtained by this process
USA
(
en)
*
-12-18
-07-25
Century Adhesives Corp.
Aqueous peroxy carbamyl group containing polymer systems and methods of their production and use
USA
(
en)
*
-09-04
-09-26
Bayer Aktiengesellschaft
Adhesive and use of the adhesive for the formation of bonds
USA
(
en)
*
-02-18
-10-24
Gencorp Inc.
Polyurethane adhesive for a surface treatment-free fiber reinforced plastic
USA
(
en)
*
-12-18
-11-28
Century Adhesives Corp.
Method of forming flexible packages and novel flexible packages
EPA2
(
en)
*
-06-02
-12-06
Minnesota Mining And Manufacturing Company
Non-hairing moisture curable compositions
USA
(
en)
*
-05-31
-01-23
The Dow Chemical Company
Modulus modification of water borne polyurethane-ureas
USA
(
en)
*
-08-15
-05-01
Bayer Aktiengessellschaft
Process for the production of aqueous polyurethane dispersions
USA
(
en)
*
-08-20
-05-08
Ashland Oil, Inc.
Primerless adhesive for fiberglass reinforced polyester substrates
USA
(
en)
*
-10-01
-05-22
Th. Goldschmidt Ag
Polyoxyalkylene ether having hydroxyl and sulfonate groups and their use in the preparation of dispersable polyurethanes
EPA1
(
en)
*
-11-15
-05-23
Reichhold Chemicals, Inc.
Water dispersible poly(urethaneureas) prepared with diisocyanate blends
DEA1
(
en)
*
-02-09
-08-23
Bollig & Kemper
Aqueous coating dispersions and their use
USA
(
en)
*
-07-05
-09-04
Uniroyal Plastics Company, Inc.
Multi-layer electrically conductive article
USA
(
en)
*
-06-23
-10-16
Union Carbide Chemicals And Plastics Company Inc.
Acid containing isocyanate-terminated prepolymers, salt prepolymers and polymers thereof
USA
(
en)
*
-09-18
-06-11
Rheox, Inc.
Water dispersible, modified polyurethane thickener with improved high shear viscosity in aqueous systems
USA
(
en)
*
-12-30
-08-13
The Sherwin-Williams Company
Water-dispersable air-drying coatings
WOA1
(
en)
*
-04-09
-10-17
Henkel Kommanditgesellschaft Auf Aktien
Household general-purpose adhesive on a polyurethane basis
DEA1
(
en)
*
-07-19
-01-23
Degussa
SURFACE-MODIFIED SILICON DIOXIDE
DEA1
(
en)
*
-08-02
-02-06
Basf Ag
PRODUCTION OF AQUEOUS POLYURETHANE DISPERSIONS
WOA1
(
en)
*
-08-06
-02-20
Uniroyal Adhesives And Sealants, Inc.
Aqueous polyurethane dispersion synthesis for adhesive thermoforming applications
USA
(
en)
*
-04-26
-06-23
Nippon Polyurethane Industry Co., Ltd.
Polyurethane resin binder for magnetic recording mediums comprising a polycarbonate polyol
WOA1
(
en)
*
-03-22
-10-01
Henkel Kommanditgesellschaft Auf Aktien
Polymer dispersions suitable for reactive systems
USA
(
en)
*
-02-05
-10-05
Bayer Aktiengesellschaft
Aqueous polyurethane dispersions and their use as laminating adhesives
USA
(
en)
*
-07-09
-08-02
Hoechst Aktiengesellschaft
Polyurethane dispersions
USA
(
en)
*
-10-15
-09-06
Bayer Aktiengesellschaft
Binder composition and its use for the production of a coating or sealing composition
USA
(
en)
*
-03-10
-04-16
R. E. Hart Labs, Inc.
Water-based, solvent-free or low voc, two-component polyurethane coatings
Family Cites Families (1)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
ATET1
(
en)
*
-09-24
-08-15
Fuller H B Licensing Financ
AQUEOUS ANIONIC POLYURETHANE DISPERSIONS
-
-
-09-09
US
US08/304,653
patent/USA/en
not_active
Expired - Fee Related
-
-
-01-04
DE
DET
patent/DET2/en
not_active
Expired - Fee Related
-
-01-04
CA
CAA
patent/CAA1/en
not_active
Abandoned
-
-01-04
NZ
NZA
patent/NZA/en
unknown
-
-01-04
MX
MXA
patent/MXA/en
not_active
Application Discontinuation
-
-01-04
KR
KRA
patent/KRB1/en
not_active
IP Right Cessation
-
-01-04
AU
AU/95A
patent/AUB2/en
not_active
Ceased
-
-01-04
AT
ATT
patent/ATET1/en
not_active
IP Right Cessation
-
-01-04
WO
PCT/US/
patent/WOA1/en
active
IP Right Grant
-
-01-04
JP
JPA
patent/JPB2/en
not_active
Expired - Lifetime
-
-01-04
ES
EST
patent/EST3/en
not_active
Expired - Lifetime
-
-01-04
EP
EPA
patent/EPB1/en
not_active
Expired - Lifetime
Patent Citations (74)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
CAA
(
en)
*
-07-25
Keberle Wolfgang
Polyurethane plastics
USA
(
en)
*
-10-14
-02-16
Dynamit Nobel Ag
Process for the polymerization of vinyl chloride with a catalyst mixture of trialkyl aluminum and boric acid trialkyl ester and a cocatalyst
USA
(
en)
*
-09-19
-11-18
Bayer Ag
Polyurethane plastics
DEB
(
en)
*
-01-16
-09-09
Bayer Ag
Process for the preparation of N- (omega-aminoalkyl) -aminoalkanesulfonic acids
FRA
(
en)
*
-02-13
-07-01
Goodyear Tire & Rubber
New polyurethane compositions and their preparation process
CHA
(
en)
*
-11-24
-12-15
Merck & Co Inc
Process for the production of a polyurethane which gives a clear solution at 25o C with at least the same volume of heavy gasoline
BEA
(
en)
*
-12-08
-04-01
GBA
(
en)
*
-10-16
-09-25
Bayer Ag
Polyurethane compositions
USA
(
en)
*
-10-23
-12-05
Bayer Ag
Process for the production of modified anionic emulsion polymers with anionic polyurethane
USA
(
en)
*
-04-29
-03-11
Bayer Ag
Preparation of cross-linked particles of polyurethane or polyurea containing ionic groups
CAA
(
en)
*
-07-18
-06-12
Keberle Wolfgang
N-(w-aminoalkane)-w'-aminoalkane sulphonic acid salts and their use as anionic structural components in the preparation of emulsifier/free polyurethane dispersions
USA
(
en)
*
-11-24
-02-18
American Cyanamid Co
Adhesive color printing system for floor coverings and other home furnishings fabrics
USA
(
en)
*
-08-29
-11-11
Ppg Industries Inc
Composition useful in making extensible films
USA
(
en)
*
-10-12
-08-29
Rhone-Progil
Polyurethane latexes from sulfonate prepolymer, aqueous chain extension process, and coated support
USA
(
en)
*
-10-16
-08-27
Ppg Industries Inc
Lactone reaction products
DEA1
(
en)
*
-08-02
-02-26
Bayer Ag
DIHYDROXYSULFONATES CONTAINING AETHER STRUCTURES
DEA1
(
en)
*
-09-28
-04-08
Bayer Ag
PROCESS FOR THE PRODUCTION OF POLYURETHANES
USA
(
en)
*
-09-28
-08-22
Bayer Aktiengesellschaft
Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols
USA
(
en)
*
-06-02
-01-03
Ppg Industries, Inc.
Water-reduced urethane coating compositions
USA
(
en)
*
-11-14
-05-30
Bayer Aktiengesellschaft
Production of water-dispersible polyurethanes having ionic groups and hydrophilic side chains
USA
(
en)
*
-12-10
-02-26
Bayer Aktiengesellschaft
Water-dispersible polyurethanes
USA
(
en)
*
-05-26
-07-04
Ppg Industries, Inc.
Polylactone-polyurethanes and aqueous dispersions thereof
USA
(
en)
*
-06-02
-04-03
Ppg Industries, Inc.
Water-reduced urethane coating compositions
USA
(
en)
*
-10-04
-05-20
Textron, Inc.
Aqueous colloidal dispersions of tertiary amine salts of urea-urethane polymers and method for manufacture
USA
(
en)
*
-10-15
-03-03
Ricoh Company, Ltd.
Pressure sensitive adhesive toner of clustered encapsulated porous particles for use in electrostatic photography
USA
(
en)
*
-11-11
-12-02
Bayer Aktiengesellschaft
Process for the preparation of polyurethanes which are dispersible in water
USA
(
en)
*
-04-18
-12-01
Bayer Aktiengesellschaft
Polyurethanes which are dispersible or soluble in water and a process for their preparation
USA
(
en)
*
-03-29
-07-07
Textron, Inc.
Water-dispersible urethane polymers and aqueous polymer dispersions
USA
(
en)
*
-12-06
-11-18
Saint-Gobain Vitrage
Adhesive in preparation of laminates
USA
(
en)
*
-04-30
-12-22
Minnesota Mining And Manufacturing Company
Aqueous solvent dispersible linear polyurethane resins
USA
(
en)
*
-12-19
-05-24
Bayer Aktiengesellschaft
Dispersions of polymers containing sulphonate groups, a process for the production thereof and their use as coating agents
USA
(
en)
*
-03-16
-05-20
Olin Corporation
Preparation of ionomers and polyurethane elastomers from carboxylic acid-containing monoether and polyether polyol addition products
USA
(
en)
*
-03-16
-07-17
Olin Corporation
Preparation of carboxylic acid-containing polyurethane prepolymers and aqueous dispersions thereof
USA
(
en)
*
-04-20
-09-10
Textron, Inc.
Water dispersible polyurethane adhesive compositions and adhesive layer formed therefrom
USA
(
en)
*
-06-20
-02-26
Mobay Chemical Corporation
Stable, aqueous dispersions of polyurethane-ureas
USA
(
en)
*
-01-19
-03-04
Bayer Aktiengesellschaft
Process for the production of polyurethanes, polyurethanes containing terminal aromatic amino groups and their use
USA
(
en)
*
-03-29
-01-13
Rohm And Haas Company
Process for preparing modified polymer emulsion adhesives
USA
(
en)
*
-12-13
-03-18
Desoto, Inc.
Aqueous water-repellent coatings
USA
(
en)
*
-09-16
-12-08
Vianova Kunstharz, A.G.
Self-crosslinking cationic paint binders containing urea and urethane groups and process of manufacture
USA
(
en)
*
-10-04
-01-31
Polyvinyl Chemicals Inc.
Coating compositions
EPA2
(
en)
*
-11-14
-05-20
Bayer Ag
Process for the immobilization of biological material, particulate coagulates containing an immobilized biological material and their use as catalysts
EPA1
(
en)
*
-03-18
-09-23
Takeda Chemical Industries, Ltd.
Thermosetting resins and electrodeposition coating compositions containing the same
USA
(
en)
*
-04-18
-05-05
E. R. Squibb & Sons, Inc.
7-oxabicycloheptane substituted amides useful in the treatment of thrombotic disease
USA
(
en)
*
-09-04
-09-26
Bayer Aktiengesellschaft
Adhesive and use of the adhesive for the formation of bonds
USA
(
en)
*
-10-01
-03-19
Th. Goldschmidt Ag
Polyoxyalkylene ethers having hydroxyl and sulfonate groups and their use in the preparation of dispersible polyurethanes
USA
(
en)
*
-10-01
-05-22
Th. Goldschmidt Ag
Polyoxyalkylene ether having hydroxyl and sulfonate groups and their use in the preparation of dispersable polyurethanes
USA
(
en)
*
-12-04
-08-16
Bayer Aktiengesellschaft
Water soluble or dispersible polyurethanes, a process for their preparation and their use for coating substrates
USA
(
en)
*
-04-15
-12-13
Basf Corporation, Inmont Division
Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics
USA
(
en)
*
-05-05
-08-09
Uniroyal Plastics Co., Inc.
Water-based thermoforming adhesives
EPA2
(
en)
*
-06-16
-12-21
W.R. Grace & Co.-Conn.
Crosslinked polyurethane emulsion, process and prepolymer for its production and process for forming coatings from said emulsion
USA
(
en)
*
-08-15
-05-01
Bayer Aktiengessellschaft
Process for the production of aqueous polyurethane dispersions
USA
(
en)
*
-08-20
-05-08
Ashland Oil, Inc.
Primerless adhesive for fiberglass reinforced polyester substrates
USA
(
en)
*
-09-18
-06-11
Rheox, Inc.
Water dispersible, modified polyurethane thickener with improved high shear viscosity in aqueous systems
EPA1
(
en)
*
-11-10
-05-17
BASF Lacke + Farben AG
Process for the preparation of macromonomers and macromonomers obtained by this process
USA
(
en)
*
-12-18
-07-25
Century Adhesives Corp.
Aqueous peroxy carbamyl group containing polymer systems and methods of their production and use
USA
(
en)
*
-12-18
-11-28
Century Adhesives Corp.
Method of forming flexible packages and novel flexible packages
USA
(
en)
*
-02-18
-10-24
Gencorp Inc.
Polyurethane adhesive for a surface treatment-free fiber reinforced plastic
USA
(
en)
*
-05-31
-01-23
The Dow Chemical Company
Modulus modification of water borne polyurethane-ureas
EPA2
(
en)
*
-06-02
-12-06
Minnesota Mining And Manufacturing Company
Non-hairing moisture curable compositions
EPA1
(
en)
*
-11-15
-05-23
Reichhold Chemicals, Inc.
Water dispersible poly(urethaneureas) prepared with diisocyanate blends
USA
(
en)
*
-12-30
-08-13
The Sherwin-Williams Company
Water-dispersable air-drying coatings
DEA1
(
en)
*
-02-09
-08-23
Bollig & Kemper
Aqueous coating dispersions and their use
USA
(
en)
*
-04-26
-06-23
Nippon Polyurethane Industry Co., Ltd.
Polyurethane resin binder for magnetic recording mediums comprising a polycarbonate polyol
USA
(
en)
*
-06-23
-10-16
Union Carbide Chemicals And Plastics Company Inc.
Acid containing isocyanate-terminated prepolymers, salt prepolymers and polymers thereof
USA
(
en)
*
-07-05
-09-04
Uniroyal Plastics Company, Inc.
Multi-layer electrically conductive article
WOA1
(
en)
*
-04-09
-10-17
Henkel Kommanditgesellschaft Auf Aktien
Household general-purpose adhesive on a polyurethane basis
DEA1
(
en)
*
-07-19
-01-23
Degussa
SURFACE-MODIFIED SILICON DIOXIDE
DEA1
(
en)
*
-08-02
-02-06
Basf Ag
PRODUCTION OF AQUEOUS POLYURETHANE DISPERSIONS
WOA1
(
en)
*
-08-06
-02-20
Uniroyal Adhesives And Sealants, Inc.
Aqueous polyurethane dispersion synthesis for adhesive thermoforming applications
USA
(
en)
*
-02-05
-10-05
Bayer Aktiengesellschaft
Aqueous polyurethane dispersions and their use as laminating adhesives
WOA1
(
en)
*
-03-22
-10-01
Henkel Kommanditgesellschaft Auf Aktien
Polymer dispersions suitable for reactive systems
USA
(
en)
*
-10-15
-09-06
Bayer Aktiengesellschaft
Binder composition and its use for the production of a coating or sealing composition
USA
(
en)
*
-07-09
-08-02
Hoechst Aktiengesellschaft
Polyurethane dispersions
USA
(
en)
*
-03-10
-04-16
R. E. Hart Labs, Inc.
Water-based, solvent-free or low voc, two-component polyurethane coatings
Non-Patent Citations (10)
* Cited by examiner, ' Cited by third party
Title
Arendt, et al., "m- and p-TMXDI: Two New Isocyanates For The Polyurethane Industry," Journal of Cellular Plastics, Dec. , pp. 376-383.
Arendt, et al., m and p TMXDI: Two New Isocyanates For The Polyurethane Industry, Journal of Cellular Plastics, Dec. , pp. 376 383.
*
NIAX Performance Polyether Polyol PWB (From Union Carbide Corporation), undated.
*
NIAX® Performance Polyether Polyol PWB- (From Union Carbide Corporation), undated.
Product Brochure for Disperscoll KA , Mobay Corporation, Jul., .
*
Product Brochure for Disperscoll KA-, Mobay Corporation, Jul., .
Product Brochure: Aqueous Polyurethane Dispersions From TMXDI (META) Aliphatic Isocyanate, Feb. .
*
Product Brochure: Aqueous Polyurethane Dispersions From TMXDI® (META) Aliphatic Isocyanate, Feb. .
Ryan, et al., "The Development of New Aqueous Polyurethane Dispersions for Coatings," Presented at the Water-Bourne, Higher Solids, and Powder Coatings Symposium Feb. 26-28, (14 pages).
Ryan, et al., The Development of New Aqueous Polyurethane Dispersions for Coatings, Presented at the Water Bourne, Higher Solids, and Powder Coatings Symposium Feb. 26 28, (14 pages).
*
Cited By (116)
* Cited by examiner, ' Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
USA
(
en)
*
-09-24
-12-30
H.B. Fuller Licensing & Financing, Inc.
Aqueous anionic poly (urethane/urea) dispersions
USA
(
en)
*
-09-09
-02-16
H. B. Fuller Licensing & Financing, Inc.
Water-based polyurethanes for footwear
USA
(
en)
*
-07-31
-06-09
Nippon Paint Co., Ltd.
Urethane prepolymer, process for producing urethane prepolymer, isocyanate compound, and polyurethane dispersion
USB2
(
en)
-02-09
-03-15
Surface Solutions Laboratories, Inc.
Articles with hydrophilic coating
USB1
(
en)
*
-02-09
-05-29
Surface Solutions Laboratories, Inc.
Articles prepared from water-based hydrophilic coating compositions
USA
(
en)
*
-03-05
-05-04
H.B. Fuller Licensing & Financing, Inc.
Aqueous polyurethane dispersions formed from polyisocyanates having a methylene bridge
USA
(
en)
*
-08-13
-09-15
H.B. Fuller Licensing & Financing, Inc.
Water-based sulfonated polymer compositions
USA
(
en)
*
-08-13
-02-29
H. B. Fuller Licensing & Financing, Inc.
Water-based sulfonated polymer compositions
USA
(
en)
*
-12-18
-12-26
Witco Corporation
Polyurethane synthesis from functional group terminated polymers containing sulfonate groups
USB1
(
en)
*
-01-30
-03-27
Rextrude Co.
Precemented welt
USB1
(
en)
-03-17
-02-19
Ameritherm, Inc.
RF active compositions for use in adhesion, bonding and coating
USB2
(
en)
-03-17
-07-29
Codaco, Inc.
RF active compositions for use in adhesion, bonding and coating
USB1
(
en)
-04-30
-12-04
Morton International, Inc.
Heat-activatable polyurethane/urea adhesive in aqueous dispersion
EPA1
(
en)
*
-04-30
-11-03
Morton International, Inc.
Heat-activatable polyurethane/urea adhesive in aqueous dispersion
USB1
(
en)
*
-06-04
-06-19
H. B. Fuller Licensing & Financing, Inc.
Dry bond film laminate employing acrylic emulsion adhesives with improved crosslinker
USB1
(
en)
-06-04
-05-22
H. B. Fuller Licensing & Financing, Inc.
Aqueous laminating adhesive composition and a method of using thereof
USA
(
en)
*
-06-17
-01-25
H.B. Fuller Licensing & Financing,Inc.
Stable aqueous polyurethane dispersions
USB1
(
en)
-12-08
-09-11
H. B. Fuller Licensing & Financing, Inc.
Process for improving hydrolysis resistance of polyurethane dispersion adhesives and bonded assemblies produced therefrom
USB1
(
en)
-12-29
-08-07
The Dow Chemical Company
Polyurethane foams prepared from mechanically frothed polyurethane dispersions
USB2
(
en)
-09-23
-11-18
Codaco, Inc.
Radio frequency (RF) heating system
USB2
(
en)
*
-11-30
-06-24
Bayer Corporation
Stable isocyanate formulations
USB1
(
en)
-02-25
-02-11
3M Innovative Properties Co.
Polyurethane-based pressure-sensitive adhesives, systems for such adhesives, articles therefrom, and methods of making
USB1
(
en)
-02-25
-11-04
3M Innovative Properties Company
Polyurethane-based adhesives, systems for such adhesives, articles therefrom, and methods of making
USA1
(
en)
*
-03-23
-02-03
Zhiqiang Zhang
Peelable coating composition
USB1
(
en)
*
-03-23
-11-23
Ashland Inc
Peelable polymeric coating composition
USB2
(
en)
*
-03-23
-03-30
Ashland Inc.
Peelable foam coating composition
USB1
(
en)
-04-05
-10-23
3M Innovative Properties Company
Low temperature thermally activated water-dispersed adhesives
USB1
(
en)
-04-05
-09-03
3M Innovative Properties Company
Water-dispersed polymer stabilizer
USB1
(
en)
-04-05
-10-30
3M Innovative Properties Company
Water-dispersed adhesive compositions
USB1
(
en)
-04-05
-04-01
3M Innovative Properties Company
Low temperature thermally activated water-dispersed adhesive compositions
USB2
(
en)
-09-21
-02-04
Cytec Technology Corp.
Low-temperature, heat-activated adhesives with high heat resistance properties
USA1
(
en)
*
-08-02
-07-10
3M Innovative Properties Company
Al2O3-rare earth oxide-ZrO2/HfO2 materials, and methods of making and using the same
USB2
(
en)
-11-02
-01-10
The Dow Chemical Company
Primer composition for promoting adhesion of a urethane adhesive to a polymeric substrate
USA1
(
en)
*
-11-02
-05-12
Chunbin Zhang
Primer composition for promoting adhesion of a urethane adhesive to a polymeric substrate
USA1
(
en)
*
-11-02
-05-08
Chunbin Zhang
Primer composition for promoting adhesion of a urethane adhesive to a polymeric substrate
CNC
(
en)
*
-01-18
-06-10
'''
Aqueous polyurethane dispersing liquid and preparation thereof as tackiness agent and coating
WOA1
(
en)
*
-01-18
-07-24
Youlu Duan
Aqueous polyurethane dispersions used as adhesives and coatings and its preparation
USA1
(
en)
*
-09-17
-07-24
Ppg Industries Ohio, Inc.
Substrates and articles of manufacture coated with a waterborne 2k coating composition
USB2
(
en)
-09-17
-03-05
Ppg Industries Ohio, Inc.
Substrates and articles of manufacture coated with a waterborne 2K coating composition
USA1
(
en)
*
-05-28
-11-23
Lonza Inc.
Quaternary ammonium salts containing non-halogen anions as anticorrosive agents
USB2
(
en)
-05-28
-07-14
Lonza Inc.
Method of applying a coating composition of quaternary ammonium salts containing non-halogen anions as anticorrosive agents
USB2
(
en)
-05-28
-07-19
Lonza Inc.
Method of inhibiting corrosion using a composition of quaternary ammonium salts containing non-halogen anions
USA1
(
en)
*
-08-13
-02-01
Valspar Sourcing, Inc.
Water-based polyurethane-polyethylene compositions
USA1
(
en)
*
-08-13
-06-25
Valspar Sourcing, Inc.
Water-dispersible polyurethane-vinyl polymer compositions
USB2
(
en)
-08-13
-06-28
Valspar Sourcing, Inc.
Water-dispersible polyurethane-vinyl polymer compositions
USA1
(
en)
*
-12-19
-06-23
3M Innovative Properties Company
Polyurethane-based pressure sensitive adhesives and methods of manufacture
USA1
(
en)
*
-01-12
-07-14
Minyu Li
Jobsite-renewable multilayer floor finish with enhanced hardening rate
USB2
(
en)
-01-12
-05-05
Ecolab, Inc.
Jobsite-renewable multilayer floor finish with enhanced hardening rate
USA1
(
en)
*
-01-12
-07-14
Ecolab Inc.
Polyurethane coating cure enhancement using zirconium carbonate
WOA1
(
en)
*
-04-13
-10-27
Lamberti S.P.A.
Adhesive aqueous compositions
USA1
(
en)
*
-12-23
-01-25
Trainham James A
Flexible polymer coating and coated flexible substrates
USB2
(
en)
-12-23
-03-15
Ppg Industries Ohio, Inc.
Color harmonization coatings for articles of manufacture comprising different substrate materials
USA1
(
en)
*
-12-23
-06-29
Rearick Brian K
Color harmonization coatings for articles of manufacture comprising different substrate materials
USA1
(
en)
*
-12-23
-06-29
Rearick Brian K
Coated compressible substrates
WOA3
(
en)
*
-04-08
-06-07
Cytec Tech Corp
Method for preparing polyurethane dispersions
WOA2
(
en)
*
-04-08
-10-19
Cytec Technology Corp.
Method for preparing polyurethane dispersions
USA1
(
en)
*
-04-08
-10-12
Ilmenev Pavel E
Method for preparing polyurethane dispersions
USA1
(
en)
*
-11-26
-05-31
Bayer Materialscience Ag
Aqueous hydroxy-functional polyester dispersions containing urethane groups
EPA1
(
en)
*
-11-26
-05-30
Bayer MaterialScience AG
Aqueous dispersions of hydroxy-functional polyester containing urethane groups
USB2
(
en)
-11-26
-07-07
Bayer Materialscience Ag
Aqueous hydroxy-functional polyester dispersions containing urethane groups
USA1
(
en)
*
-01-16
-06-18
Nicola Rehnberg
Low protonation constant hydroxy acids
WOA1
(
en)
-01-16
-07-19
Bwe I Malmö Ab
Low protonation constant hydroxy acids
USB2
(
en)
-01-16
-04-30
Bwe I Malmo Ab
Low protonation constant hydroxy acids
USB2
(
en)
-05-03
-07-14
Surface Solutions Laboratories
Coating resins and coating with multiple crosslink functionalities
USA1
(
en)
*
-09-22
-03-27
Steven Michael Baxter
Polymer compositions containing polyurethanes
CNB
(
en)
*
-11-01
-11-03
'''''''''''''
Polyurethane prepolymer, aquosity polyurethane binder and uses thereof
USA1
(
en)
*
-03-27
-10-01
Ppg Industries Ohio, Inc.
Polycarbodiimides
CNB
(
en)
*
-02-10
-11-30
''''''''''
Method of preparing polyurethane resin for new shoe leather
USB2
(
en)
*
-09-25
-09-10
Henkel Ag & Co. Kgaa
Water-based adhesive for lamination of polymers to metal substrates
USA1
(
en)
*
-09-25
-03-31
Mcgee John D
Water-based adhesive for lamination of polymers to metal substrates
CNA
(
en)
*
-10-29
-07-11
''''''''''
Aqueous formulations based on crystalline or semi-crystalline polyurethane polymers
CNB
(
en)
*
-10-29
-12-24
''''''''''
Aqueous formulations based on crystalline or semi-crystalline polyurethane polymers
USB2
(
en)
-04-09
-06-03
Bayer Materialscience Llc
Two-component waterborne polyurethane coatings
USB2
(
en)
-02-18
-02-10
Eastern Michigan University
Bio-based polyurethane dispersion compositions and methods
USB2
(
en)
*
-09-22
-10-06
Lintec Corporation
Flame retardant adhesive sheet
USA1
(
en)
*
-09-22
-05-15
Lintec Corporation
Flame retardant adhesive sheet
CNA
(
en)
*
-05-23
-09-25
''''''''''
Production method of waterborne polyurethane used for artificial leather bonding resin
USB2
(
en)
-07-30
-10-31
H.B. Fuller Company
Polyurethane adhesive film
USB2
(
en)
*
-12-03
-05-15
Rohm And Haas Company
Aqueous polyurethane dispsersions
USB2
(
en)
-05-05
-04-07
Resinate Materials Group, Inc.
Polyester polyols from thermoplastic polyesters and dimer fatty acids
USB2
(
en)
-05-05
-07-09
Resinate Materials Group, Inc.
Polyester polyols from thermoplastic polyesters and dimer fatty acids
USB2
(
en)
-05-05
-12-12
Resinate Materials Group, Inc.
Polyester polyols from thermoplastic polyesters and dimer fatty acids
JPWOA1
(
en)
*
-06-20
-05-25
''''''''
Aqueous polyurethane resin dispersion
USB2
(
en)
-08-20
-09-17
Resinate Materials Group, Inc.
High recycle content polyester polyols
WOA1
(
en)
-10-29
-05-06
Resinate Materials Group, Inc.
High recycle content polyester polyols from hydroxy-functional ketal acids, esters or amides
USB2
(
en)
-12-15
-04-17
H.B. Fuller Company
Reactive film adhesives with enhanced adhesion to metallic surfaces
USB2
(
en)
-12-15
-05-01
H.B. Fuller Company
Reactive adhesive with enhanced adhesion to metallic surfaces
USB2
(
en)
-01-21
-05-28
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
USB2
(
en)
-01-21
-09-05
Resinate Materials Group, Inc.
High recycle content polyols from thermoplastic polyesters and lignin or tannin
WOA1
(
en)
*
-01-21
-07-28
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
USB2
(
en)
-01-21
-11-01
Resinate Materials Group, Inc.
High recycle content polyols from thermoplastic polyesters and lignin or tannin
USB2
(
en)
-01-21
-06-05
Resinate Materials Group, Inc.
High recycle content polyols from thermoplastic polyesters and lignin or tannin
USB2
(
en)
-01-30
-09-05
Resinate Materials Group, Inc.
Integrated process for treating recycled streams of PET and PTT
USB2
(
en)
-01-30
-07-25
Resinate Materials Group, Inc.
Integrated process for treating recycled PET and PTT materials
USB2
(
en)
-01-30
-11-06
Resinate Materials Group, Inc.
Integrated process for treating recycled streams of PET and PTT
USB2
(
en)
-03-12
-10-20
Henkel Ag & Co. Kgaa
Aqueous polyurethane dispersions
WOA1
(
en)
*
-03-12
-09-15
Henkel Ag & Co. Kgaa
Aqueous polyurethane dispersions
WOA1
(
en)
-03-20
-09-29
Resinate Materials Group, Inc.
Cycloaliphatic polyester polyols from thermoplastic polyesters
USB2
(
en)
-03-20
-08-07
Resinate Materials Group, Inc.
Cycloaliphatic polyester polyols from thermoplastic polyesters
USB2
(
en)
-03-20
-12-20
Resinate Materials Group, Inc.
Cycloaliphatic polyester polyols from thermoplastic polyesters
USB2
(
en)
-04-14
-03-02
Resinate Materials Group, Inc.
Polyester polyols with increased clarity
WOA1
(
en)
*
-09-21
-03-30
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
EPA1
(
en)
*
-09-21
-03-17
3M Innovative Properties Company
Chemical resistant polyurethane adhesive
CNA
(
en)
*
-07-05
-09-07
''''''
Biomass-resource-modified water-based polyurethane emulsion and preparation method thereof
USB2
(
en)
-02-28
-04-18
3M Innovative Properties Company
Polyurethane adhesive with chemical resistant
USB2
(
en)
-03-03
-04-12
Carlisle Construction Materials, LLC
Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom
WOA1
(
en)
-03-03
-09-07
Resinate Materials Group, Inc.
Sustainable, energy-curable polyester polyols and coatings or rigid foams therefrom
USB2
(
en)
*
-10-11
-10-29
Eastman Kodak Company
Method of inkjet printing
USA1
(
en)
*
-10-11
-04-11
Eastman Kodak Company
Method of inkjet printing
USB2
(
en)
-12-21
-09-21
Covestro Deutschland Ag
Frost-resistant adhesives based on polyisocyanates
WOA1
(
en)
-12-21
-06-27
Covestro Deutschland Ag
Frost-resistant adhesives based on polyisocyanates
USB2
(
en)
-05-04
-12-19
Carlisle Construction Materials, LLC
Polyurethane dispersions and their use to produce coatings and adhesives
USB2
(
en)
-11-19
-08-22
Covestro Llc
Polyisocyanate resins
USB2
(
en)
-11-19
-08-06
Covestro Llc
Polyisocyanate resins
CNA
(
en)
*
-01-11
-05-28
''''''''''''''
High-temperature-resistant water polyurethane, preparation method thereof, water-based polyurethane adhesive and preparation method thereof
CNA
(
en)
*
-12-20
-04-22
''''
Sizing agent for preventing Lycra cotton yarn from bonding and sizing process thereof
Also Published As
Publication number
Publication date
NZA
(
en)
-12-19
CAA1
(
en)
-03-14
AUB2
(
en)
-11-06
EPA4
(
en)
-07-09
JPHA
(
en)
-06-30
EST3
(
en)
-10-01
DED1
(
en)
-08-12
DET2
(
en)
-02-10
KRB1
(
en)
-07-15
EPB1
(
en)
-07-07
WOA1
(
en)
-03-14
JPB2
(
en)
-10-04
AUA
(
en)
-03-27
ATET1
(
en)
-07-15
MXA
(
en)
-06-28
EPA1
(
en)
-06-25
KRA
(
en)
-10-09
Similar Documents
Publication
Publication Date
Title
USA
(
en)
-03-04
Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
USA
(
en)
-03-11
Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
MXPAA
(
en)
-06-01
Adhesive compositions of aqueous dispersions depoliuretano with improved resistance to the ac
USA
(
en)
-06-10
Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat-and water-resistance
USA
(
en)
-12-30
Aqueous anionic poly (urethane/urea) dispersions
AUB2
(
en)
-08-20
Aqueous non-gelling, anionic polyurethane dispersions and process for their manufacture
JPB2
(
en)
-03-11
Anionic aqueous polyurethane dispersion
KRB1
(
en)
-06-10
Aqueous solutions and dispersions of polysocyanate polyadditionproducts, process for the preparation of the same
USA
(
en)
-01-25
Stable aqueous polyurethane dispersions
DET2
(
en)
-02-15
Polyurethane resin water dispersion and aqueous polyurethane adhesive
AUB2
(
en)
-12-23
Laminating adhesives for flexible packaging
EPB1
(
en)
-03-28
Cold contact adhesives
USA1
(
en)
-09-24
Dispersion adhesives
USA
(
en)
-02-16
Water-based polyurethanes for footwear
EPA1
(
en)
-08-17
Curable polyurethane dispersions
TWIB
(
en)
-06-01
Adhesives
USB2
(
en)
-05-22
Aqueous hybrid bonding composition and process
MXPAA
(
en)
-11-09
Reduced solvent process for the preparation of polyurethane dispersions with improved heat resistance and solvent
Legal Events
Date
Code
Title
Description
-11-28
AS
Assignment
Owner name:
H.B. FULLER LICENSING & FINANCING, INC., MINNESOTA
For more information, please visit our website.
Free format text:
ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DUAN, YOULU;STAMMLER, SONJA;REEL/FRAME:/;SIGNING DATES FROM TO
-12-09
FEPP
Fee payment procedure
Free format text:
PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
-09-01
FPAY
Fee payment
Year of fee payment:
4
You will get efficient and thoughtful service from HumenChem.
-09-22
REMI
Maintenance fee reminder mailed
-03-04
LAPS
Lapse for failure to pay maintenance fees
-04-06
LAPS
Lapse for failure to pay maintenance fees
Free format text:
PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
-04-06
STCH
Information on status: patent discontinuation
Free format text:
PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362
-05-03
FP
Lapsed due to failure to pay maintenance fee
Effective date: