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US4147679A Expired / Lapsed US ⏱️ 0.0 years remaining

Water-reduced urethane coating compositions

Assignee: PPG Industries Inc
•
Filing: 1977-11-21
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Granted: 1979-04-03
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Expires: 1997-11-21
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Abstract

Abstract A water-diluted, ungelled, non-sedimenting polyurethane and a process for preparing such a polyurethane in an aqueous medium is disclosed. High molecular weight thermoplastic products are obtained by chain extending in aqueous medium an NCO polymer having a salt group equivalent weight of 6000 or less and substantially free of reactive hydrogen. The average functionality and equivalent ratio of the polyisocyanate and active hydrogen-containing materials used in making the NCO polymer, as well as the functionality of the chain extender, are carefully controlled so as to get high molecular weight ungelled products. Thermosetting compositions can be made by adding curing agent to the chain extended material. Curing agents can also be incorporated into the polymer molecule either in the making of the partially reacted NCO-containing prepolymer or by further reaction with the partially reacted NCO-containing prepolymer. The water-dispersed polyurethanes of the present invention are excellent film formers, capable of making coatings with a wide spectrum of desirable properties. In addition, they can be added to other water-compatible compositions to improve flexibility, hardness, drying and other coating properties.

Inventors

  • 👤 Roger L. Scriven
  • 👤 Wen-Hsuan Chang

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-23 21:17
CPC Classifications
C; C09; C09D; C09D175/00; C09D175/04; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/0804; C08G18/0833; C08G18/10; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31678; Y10T442/00; Y10T442/20; Y10T442/2369

Claims Analysis

Total Claims: 35
Claim 1
Independent Claim 252 words
A non-sedimenting aqueous dispersion which is emulsifiable in the absence of added emulsifier of an ungelled polyurethane having a finely particulated dispersed phase of less than 10 microns which requires only mild agitation for dispersion formed by reacting in aqueous medium in which water is the principal ingredient: (A) NCO-containing polymer containing anionic salt groups having monovalent counter ions and having a salt group equivalent weight of 200 to 5000 being substantially free of highly active hydrogens, and having a viscosity of 50 to 10,000 centipoises, said polymer formed from: (1) an organic polyisocyanate and (2) an active hydrogen-containing material containing at least 2 active hydrogens per molecule, said organic polyisocyanate and said active hydrogen-containing compound containing a total of not more than 1 gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and active hydrogen-containing material; the equivalent ratio of NCO in (1) to active hydrogen in (2) being at least about 4/3; the anionic salt groups introduced into said NCO-containing polymer through the active hydrogen-containing material (2); (B) active hydrogen-containing material in which the active hydrogens are more reactive with NCO groups than water to form a polyurethane having an intrinsic viscosity less than 4.0 deciliters per gram; said aqueous dispersion containing at least 15 percent by weight aqueous medium based on total weight of ungelled polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water with co-solvent constituting the remainder of the aqueous medium.
Claim 2
Dependent Claim 252 words
A non-sedimenting aqueous dispersion which is emulsifiable in the absence of added emulsifier of an ungelled polyurethane having a finely particulated dispersed phase of less than 10 microns which requires only mild agitation for dispersion formed by reacting in aqueous medium in which water is the principal ingredient: (A) NCO-containing polymer containing anionic salt groups having monovalent counter ions and having a salt group equivalent weight of 200 to 5000 being substantially free of highly active hydrogens, and having a viscosity of 50 to 10,000 centipoises, said polymer formed from: (1) an organic polyisocyanate and (2) an active hydrogen-containing material containing at least 2 active hydrogens per molecule, said organic polyisocyanate and said active hydrogen-containing compound containing a total of not more than 1 gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and active hydrogen-containing material; the equivalent ratio of NCO in (1) to active hydrogen in (2) being at least about 4/3; the anionic salt groups introduced into said NCO-containing polymer through the active hydrogen-containing material (2); (B) active hydrogen-containing material in which the active hydrogens are more reactive with NCO groups than water to form a polyurethane having an intrinsic viscosity less than 4.0 deciliters per gram; said aqueous dispersion containing at least 15 percent by weight aqueous medium based on total weight of ungelled polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water with co-solvent constituting the remainder of the aqueous medium.
Claim 3
Dependent Claim 16 words
The dispersion of claim 1 in which the anionic salt groups are carboxylic acid salt groups.
Claim 4
Dependent Claim 22 words
The dispersion of claim 1 in which the NCO-containing polymer contains no more than 50 percent by weight of ethylene oxide moieties.
Claim 5
Dependent Claim 36 words
The dispersion of claim 1 in which the NCO-containing polymer is dissolved in about 5 to 60 percent by weight organic solvent; the percentage by weight being based on total weight of solvent and NCO-containing polymer.
Claim 6
Dependent Claim 26 words
The dispersion of claim 4 in which the organic solvent is water-soluble and at least part of the solvent has a boiling point above 150° C.
Claim 7
Dependent Claim 24 words
The dispersion of claim 1 in which either the organic polyisocyanate, the active hydrogen-containing material (2) or the active hydrogen-containing material (B) is trifunctional.
Claim 8
Dependent Claim 18 words
The dispersion of claim 1 in which the organic polyol contains at least in part a polyester polyol.
Claim 9
Dependent Claim 26 words
The dispersion of claim 6 in which the equivalent ratio of organic polyisocyanate to active hydrogen-containing compound groups is within the range of 6 to 1.8:1.
Claim 10
Dependent Claim 19 words
The dispersion of claim 1 in which the dispersed phase has a particle size of 5 microns or less.
Claim 11
Dependent Claim 36 words
The dispersion of claim 1 in which the NCO-containing polymer is reacted in said aqueous medium with a polyfunctional active hydrogen-containing compound having at least two hydrogens which are more reactive with NCO groups than water.
Claim 12
Dependent Claim 14 words
The dispersion of claim 1 in which (B) is a primary or secondary polyamine.
Claim 13
Dependent Claim 12 words
The dispersion of claim 11 in which the polyamine is a diamine.
Claim 14
Dependent Claim 19 words
The dispersion of claim 1 in which (B) is a hydrazine, a substituted hydrazine or a hydrazine reaction product.
Claim 15
Dependent Claim 14 words
The dispersion of claim 11 in which the active hydrogen-containing compound is an alkanolamine.
Claim 16
Dependent Claim 14 words
The dispersion of claim 1 in which the polyruethane contains unsaturated fatty acid moieties.
Claim 17
Dependent Claim 13 words
The dispersion of claim 1 which contains curing groups in the polymer molecule.
Claim 18
Dependent Claim 32 words
The dispersion of claim 16 in which the curing groups are selected from the class consisting of N-alkoxymethyl moieties, blocked isocyanate moieties, masked isocyanate moieties, alkoxysilane moieties, and moieties containing ethylenic unsaturation.
Claim 19
Dependent Claim 20 words
The dispersion of claim 16 which is applied as a coating and treated with microwave with or without ultraviolet radiation.
Claim 20
Dependent Claim 274 words
An aqueous coating composition comprising: (A) a non-sedimenting aqueous dispersion which is emulsifiable in the absence of added emulsifier of an ungelled NCO-free polyurethane having a finely particulated dispersed phase of less than 10 microns which requires only mild agitation for dispersion formed by reacting in aqueous medium in which water is the principal ingredient: (1) an NCO-containing polymer containing anionic salt groups having a salt group equivalent weight of 200 to 5000 and having monovalent counter ions being substantially free of reactive active hydrogens and having a viscosity of 50 to 10,000 centipoises, said polymer formed from: (i). an organic polyisocyanate and (ii). an organic material containing at least two active hydrogens said organic polyisocyanate and said organic active hydrogen-containing material containing a total of not more than one gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and organic material containing at least 2 active hydrogens; said NCO-containing polymer containing an equivalent ratio of NCO in (i) to active hydrogen in (ii) of at least about 4/3, the anionic salt groups introduced into said NCO-containing polymer through (ii), (2) an active hydrogen-containing compound having at least one hydrogen more reactive with NCO groups than water having an average functionality of 2 or less to form a polyurethane having an intrinsic viscosity lower than 2.0 deciliters per gram; said aqueous dispersion containing at least 15 percent by weight aqueous medium based on total weight of polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water with co-solvent constituting the remainder of the aqueous medium; (B) a curing agent.
Claim 21
Dependent Claim 274 words
An aqueous coating composition comprising: (A) a non-sedimenting aqueous dispersion which is emulsifiable in the absence of added emulsifier of an ungelled NCO-free polyurethane having a finely particulated dispersed phase of less than 10 microns which requires only mild agitation for dispersion formed by reacting in aqueous medium in which water is the principal ingredient: (1) an NCO-containing polymer containing anionic salt groups having a salt group equivalent weight of 200 to 5000 and having monovalent counter ions being substantially free of reactive active hydrogens and having a viscosity of 50 to 10,000 centipoises, said polymer formed from: (i). an organic polyisocyanate and (ii). an organic material containing at least two active hydrogens said organic polyisocyanate and said organic active hydrogen-containing material containing a total of not more than one gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and organic material containing at least 2 active hydrogens; said NCO-containing polymer containing an equivalent ratio of NCO in (i) to active hydrogen in (ii) of at least about 4/3, the anionic salt groups introduced into said NCO-containing polymer through (ii), (2) an active hydrogen-containing compound having at least one hydrogen more reactive with NCO groups than water having an average functionality of 2 or less to form a polyurethane having an intrinsic viscosity lower than 2.0 deciliters per gram; said aqueous dispersion containing at least 15 percent by weight aqueous medium based on total weight of polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water with co-solvent constituting the remainder of the aqueous medium; (B) a curing agent.
Claim 22
Dependent Claim 14 words
The composition of claim 19 in which the polyurethane of (A) contains hydroxyl groups.
Claim 23
Dependent Claim 24 words
The composition of claim 19 in which the curing agent is selected from the class consisting of aminoplast, polyisocyanates, phenolic resin or epoxy-containing materials.
Claim 24
Dependent Claim 13 words
The composition of claim 19 in which the polyurethane contains reactive amine groups.
Claim 25
Dependent Claim 17 words
The composition of claim 22 in which the curing agent is an epoxy-containing material or a polyisocyanate.
Claim 26
Dependent Claim 20 words
The composition of claim 19 which is applied as a coating and treated with microwave with or without ultraviolet radiation.
Claim 27
Dependent Claim 13 words
The dispersion of claim 1 which is applied as a coating by electrodeposition.
Claim 28
Dependent Claim 14 words
The dispersion of claim 1 which is applied as a coating by electrostatic spraying.
Claim 29
Dependent Claim 19 words
The dispersion of claim 1 in which salt formation takes place when the prepolymer is dispersed in aqueous medium.
Claim 30
Dependent Claim 21 words
The dispersion of claim 1 in which the NCO-containing polymer solution has a viscosity of from about 100 to 5000 centipoises.
Claim 31
Dependent Claim 51 words
The dispersion of claim 1 in which the aqueous dispersion contains 20 to 70 percent by weight aqueous medium based on total weight of polyurethane in aqueous medium of which at least 40 percent by weight of the aqueous medium is water with co-solvents constituting the remainder of the aqueous medium.
Claim 32
Dependent Claim 28 words
The dispersion of claim 1 in which the active hydrogens in (2) are selected from the class consisting of --OH, --SH, --NH, and --NH 2 including mixed groups.
Claim 33
Independent Claim 315 words
A method of forming a non-sedimenting aqueous dispersion of an ungelled polyurethane which is emulsifiable in the absence of added emulsifier comprising: (A) preparing an NCO-containing polymer containing anionic salt groups or groups which are readily converted to anionic salt groups in aqueous medium, said salt groups having monovalent counter ions, said NCO-containing polymer being formed from (1) an organic polyisocyanate and (2) an active hydrogen-containing material containing at least two active hydrogens per molecule, said organic polyisocyanate and said active hydrogen-containing material containing a total of not more than one gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and active hydrogen-containing material; the equivalent ratio of NCO in (1) to active hydrogens in (2) being at least about 4/3; the anionic salt groups or groups which are readily converted to anionic salt groups introduced into said NCO-containing polymer through the active hydrogen-containing material (2); said NCO-containing polymer being substantially free of highly active hydrogens and having a viscosity of 50 to 10,000 centipoises; (B) dispersing said NCO-containing prepolymer in aqueous medium in which water is the principal ingredient, said NCO-containing polymer having an anionic salt group equivalent weight of from 200 to 5000 in said aqueous medium; (C) chain extending the dispersed NCO-containing prepolymer with an active hydrogen-containing material in which the active hydrogens are more reactive with the NCO groups than water to form a polyurethane having an intrinsic of less than 4.0 deciliters per gram; said chain extension occurring to form an ungelled polyurethane dispersion having a finely particulated dispersed phase of less than 10 microns and in which the dispersion contains at least 15 percent by weight aqueous medium based on total weight of the ungelled polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water, the co-solvent constituting the remainder of the aqueous medium.
Claim 34
Independent Claim 315 words
A method of forming a non-sedimenting aqueous dispersion of an ungelled polyurethane which is emulsifiable in the absence of added emulsifier comprising: (A) preparing an NCO-containing polymer containing anionic salt groups or groups which are readily converted to anionic salt groups in aqueous medium, said salt groups having monovalent counter ions, said NCO-containing polymer being formed from (1) an organic polyisocyanate and (2) an active hydrogen-containing material containing at least two active hydrogens per molecule, said organic polyisocyanate and said active hydrogen-containing material containing a total of not more than one gram-mole of compounds having a functionality of 3 or more per 500 grams of organic polyisocyanate and active hydrogen-containing material; the equivalent ratio of NCO in (1) to active hydrogens in (2) being at least about 4/3; the anionic salt groups or groups which are readily converted to anionic salt groups introduced into said NCO-containing polymer through the active hydrogen-containing material (2); said NCO-containing polymer being substantially free of highly active hydrogens and having a viscosity of 50 to 10,000 centipoises; (B) dispersing said NCO-containing prepolymer in aqueous medium in which water is the principal ingredient, said NCO-containing polymer having an anionic salt group equivalent weight of from 200 to 5000 in said aqueous medium; (C) chain extending the dispersed NCO-containing prepolymer with an active hydrogen-containing material in which the active hydrogens are more reactive with the NCO groups than water to form a polyurethane having an intrinsic of less than 4.0 deciliters per gram; said chain extension occurring to form an ungelled polyurethane dispersion having a finely particulated dispersed phase of less than 10 microns and in which the dispersion contains at least 15 percent by weight aqueous medium based on total weight of the ungelled polyurethane and aqueous medium of which at least 30 percent by weight of the aqueous medium is water, the co-solvent constituting the remainder of the aqueous medium.
Claim 35
Dependent Claim 23 words
The method of claim 31 in which the anionic salt groups are formed when the NCO-containing polymer is dispersed in the aqueous medium.

References Cited (Backward Citations)

US3488272A Cited
US3539483A Cited
GB1278426A Cited
US3709860A Cited
US3686108A Cited
US3799854A Cited
CA919329A Cited
US3804786A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1982-04-02 1982-10-02 1983-04-03 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1986-04-02 1986-10-02 1987-04-03 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1990-04-02 1990-10-02 1991-04-03 $7700.00 Window Closed / Lapsed

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