# US 5,352,733 A · Water based, solvent free, two component aliphatic polyurethane coating > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,352,733 A - Document ID: US5352733A - Status: Granted - Kind: A - Application number: 08/028,966 - Filed: 1993-03-10 - Granted: 1994-10-04 - Earliest claimed: 1993-03-10 - Assignees: R. E. Hart Labs, Inc. - Inventors: Richard E. Hart - Web page: https://patentgrep.com/patent/US5352733A ## CPC - C08G 18/0823: {containing carboxylate salt groups or groups forming them} - C08G 18/2865: {Compounds having only one primary or secondary amino group; Ammonia} - C08G 18/4018: {Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48} - C08G 18/4202: {Two or more polyesters of different physical or chemical nature (C08G18/44 takes precedence)} - C08G 18/4263: {containing carboxylic acid groups} - C08G 18/4887: {containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids} - C08G 18/6254: {Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups} - C08G 18/6523: {Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38} - C08G 18/6607: {with compounds of group C08G18/3203} - C08G 18/6611: {having at least three hydroxy groups} - C09D 175/06: from polyesters - C09D 175/12: from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group - Y10T 428/31551: Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.] - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A water based, solvent free, two component polyurethane-polyurea dispersion containing up to 65% solids. The first component is a polyester-polyol phase and an aqueous amine phase mixture. The polyester-polyol is a combination of modified polyester-polyols, low viscosity polyether or polyester-polyols, chain extending low molecular weight polyols, neutralizing amines and a detergent. It has a solids content of 90-100% and is totally hydroxyl functional with a carboxylic acid number of 10 and 50, an hydroxyl number of 180 and 300, an equivalent weight range of 165 and 365 and a viscosity of 600-1500 cps at 25.degree. C. The amine phase is an combination of neutralizing and chain extending amines having ratios preformulated to provide a balanced chain extending cross-linking reaction in aqueous phase with--NCO reactive groups. The aqueous amine blend has an equivalent weight of 40 to 50 and a solids content of 40-60%. The polyester-polyol and amine phases are combined in water at room temperature to form a aqueous component having a solids content of 33 to 48% and has an equivalent ratio between polyester-polyol phase and amine phase of 1.75:1 to 2.25:2. The second component is a 100% solids aliphatic isocyanate having a viscosity of between 1000-3500 cps at 25.degree. C. and provides an NCO to functional groups in the polyester-polyol/amine component ratio of between about 1:1.3 to 1:1.7. This solvent free dispersion dries to a film coating having properties equal to conventional solvent based polyurethane coatings. ## Claims ### Claim 1 A water based, solvent free, two component polyurethane-polyurea dispersion having a solids content of up to 65% by weight comprising the reaction product of an organic solvent free polyester-polyol blend/amine blend aqueous phase component and a 100 percent solids aliphatic polyisocyanate component comprising: a) a polyester-polyol blend/amine blend aqueous phase component having a solids content of between about 33 and 48%, a viscosity of between about 100 and 250 cps at 25.degree. C. and a polyester-polyol blend to amine blend equivalent ratio of between about 1.75:1 to 2.25:1 comprising an aqueous dispersion of: 1) a polyester-polyol blend containing (a) from 0.33 to 0.67 equivalents of a modified polyester-polyol comprising the reaction product of polyhydric polyols with a member selected from the group consisting of polycarboxyic acids and poycarboxylic anhydrides containing from 1 to 2% by weight of a trihydric polyol and from about 10-15% by weight of a polyfunctional diol containing a carboxylic acid group, said modified polyester-polyol having a molecular weight of between about 1000 to 2000, an equivalent weight of between about 750 to 850 and a hydroxyl number of between about 55 to 100; (b) 0.45 to 0.75 equivalents of a low viscosity polyol comprising a member selected from the group consisting of aliphatic polyether-polyols and polyester-polyols and trihydric polyol modified polyester-polyols having an equivalent weight of between about 150 and 200 and an hydroxyl number of between about 300 and 350; (c) 0.33 to 0.67 equivalents of a low molecular weight chain extending diol or triol having from three to eight carbon atoms and having a equivalent weight of from about 30 to 60; (d) 0.15 to 0.33 equivalents of a first neutralizing amine selected from the group consisting of diethanol amine and triethanol amine and mixtures thereof; (e) 0.15 to 0.33 equivalents of a second neutralizing amine selected from the group consisting of 2-amino-2-methyl-1-propanol and tris(hydroxymethyl)aminomethane; and (f) 1-5% by weight of a non-reactive non-ionic detergent; said polyester-polyol blend having a solids content of between 90 and 100%, an equivalent weight of between about 165 to 365; an hydroxyl number of between about 180 to 300, an acid number of between about 10 and 50 and a viscosity of between about 600 to 1500 cps at 25.degree. C. and, 2) an aqueous amine blend containing (g) 0.15 to 0.33 equivalents of a first neutralizing amine selected from the group consisting of diethanol amine and triethanol amine and mixtures thereof; (h) 0.15 to 0.33 equivalents of a second neutralizing amine selected from the group consisting of 2-amino-2-methyl-1-propanol and tris (hydroxymethyl) aminomethane; (i) 0.045 to 0.075 equivalents of a first chain extending amine consisting of a lower dialkanolamine containing from about 2 to 4 carbon atoms; (j) 0.045 to 0.075 equivalents of a second chain extending amine comprising a member selected from the group consisting of diethylenetriamine and triethylenetetraamine; (k) 0.15 to 0.25 equivalents of a third chain extending amine consisting of 2-methylpentamethylenediamine; and (l) 0.15 to 0.3 equivalents of a fourth chain extending amine consisting of 1,3-diaminopentane; said amine blend having an equivalent weight of between about 40 and 50 and containing a solids content of between about 40 and 60% by weight, and b) an aliphatic polyisocyanate having a viscosity of between 1000-3500 cps at 25.degree. C.; wherein the ratio between isocyanate component equivalents and polyester-polyol/amine component equivalents is between about 1.3:1 to 1.7:1. ### Claim 2 (depends on 1) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 1 wherein said modified polyester-polyol is a modified hexaneadipate diol saturated polyester polyol, said trihydric alcohol is an .alpha.,.alpha.,.alpha.-trimethylol alkane having the formula: ##STR3## wherein R is an alkyl group of 1 to 8 carbon atoms and said polyfunctional diol containing a carboxylic acid group is a .alpha.,.alpha.-dimethylol alkanoic acid of the formula: ##STR4## wherein R is an alkyl group of 1 to 8 carbon atoms. ### Claim 3 (depends on 2) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 2 wherein said hexaneadipate diol is a 1,4-hexaneadipate diol, said .alpha.,.alpha.,.alpha.-trimethylol alkane is a member selected from the group consisting of trimethylolethane, trimethylolpropane and trimethylolbutane and said .alpha.,.alpha.-dimethylol alkanoic acid is a member selected from the group consisting of 2,2-dimethylol propionic acid, 2,2,-dimethylol butyric acid, 2,2-dimethylol pentanoic acid. ### Claim 4 (depends on 3) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 3 wherein said low viscosity polyol is a member selected from the group consisting of polyester-polyols and trihydric polyol modified polyester-polyols having incorporated therein between about 2 and 10% of .alpha.,.alpha.,.alpha.-trimethylolalkane selected from the group consisting of trimethylolethane, trimethylolpropane and trimethylolbutane. ### Claim 5 (depends on 4) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 4 wherein said .alpha.,.alpha.,.alpha.-trimethylol alkane is trimethylolethane and said .alpha.,.alpha.-dimethylol alkanoic acid is 2,2-dimethylol propionic acid. ### Claim 6 (depends on 5) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 5 wherein said low molecular weight chain extending diol or triol is 1,4-butanediol. ### Claim 7 (depends on 6) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 6 wherein said first neutralizing amine is a mixture comprising a major amount of triethanol amine and a minor amount of diethanol amine. ### Claim 8 (depends on 7) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 7 wherein said second neutralizing amine is 2-amino-2-methyl-1-propanol. ### Claim 9 (depends on 8) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 8 wherein said first neutralizing amine is a mixture comprising about 85% of triethanol amine and 15% of diethanol amine. ### Claim 10 (depends on 9) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 9 wherein said non-ionic detergent is a 100% active polymeric dispersant with nonionic anchor groups. ### Claim 11 (depends on 9) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 9 wherein said first chain extending amine is diethanol amine. ### Claim 12 (depends on 11) A water based, solvent free, two component polyurethane-polyurea dispersion according to claim 11 wherein said second chain extending amine is diethylenetriamine. ### Claim 13 A substrate having coated on at least one surface thereof a cured and crosslinked polyurethane-polyurea coating obtained by applying to said substrate a thin layer of a water based, solvent free, two component polyurethane-polyurea dispersion having a solids content of up to 65% by weight comprising the reaction product of an organic solvent free polyester-polyol blend/amine blend aqueous phase component and a 100 percent solids aliphatic polyisocyanate component comprising: a) a polyester-polyol blend/amine blend aqueous phase component having a solids content of between about 33 and 48%, a viscosity of between about 100 and 250 cps at 25.degree. C. and a polyester-polyol blend to amine blend equivalent ratio of between about 1.75:1 to 2.25:1 comprising an aqueous dispersion of: 1) a polyester-polyol blend containing (a) from 0.33 to 0.67 equivalents of a modified polyester-polyol comprising the reaction product of polyhydric polyols with a member selected from the group consisting of polycarboxyic acids and polycarboxylic anhydrides containing from 1 to 2% by weight of a trihydric polyol and from about 10-15% by weight of a polyfunctional diol containing a carboxylic acid group, said modified polyester-polyol having a molecular weight of between about 1000 to 2000, an equivalent weight of between about 750 to 850 and a hydroxyl number of between about 55 to 100; (b) 0.45 to 0.75 equivalents of a low viscosity polyol comprising a member selected from the group consisting of aliphatic polyether-polyols and polyester-polyols and trihydric polyol modified polyester-polyols having an equivalent weight of between about 150 and 200 and an hydroxyl number of between about 300 and 350; (c) 0.33 to 0.67 equivalents of a low molecular weight chain extending diol or triol having from three to eight carbon atoms and having a equivalent weight of from about 30 to 60; (d) 0.15 to 0.33 equivalents of a first neutralizing amine selected from the group consisting of diethanol amine and triethanol amine and mixtures thereof; (e) 0.15 to 0.33 equivalents of a second neutralizing amine selected from the group consisting of 2-amino-2-methyl-1-propanol and tris(hydroxymethyl)aminomethane; and (f) 1-5% by weight of a non-reactive non-ionic detergent; said polyester-polyol blend having a solids content of between 90 and 100%, an equivalent weight of between about 165 to 365; an hydroxyl number of between about 180 to 300, an acid number of between about 10 and 50 and a viscosity of between about 600 to 1500 cps at 25.degree. C. and, 2) an aqueous amine blend containing (g) 0.15 to 0.33 equivalents of a first neutralizing amine selected from the group consisting of diethanol amine and triethanol amine and mixtures thereof; (h) 0.15 to 0.33 equivalents of a second neutralizing amine selected from the group consisting of 2-amino-2-methyl-1-propanol and tris (hydroxymethyl) aminomethane; (i) 0.045 to 0.075 equivalents of a first chain extending amine consisting of a lower dialkanolamine containing from about 2 to 4 carbon atoms; (j) 0.045 to 0.075 equivalents of a second chain extending amine comprising a member selected from the group consisting of diethylenetriamine and triethylenetetraamine; (k) 0.15 to 0.25 equivalents of a third chain extending amine consisting of 2-methylpentamethylenediamine; and (l) 0.15 to 0.3 equivalents of a fourth chain extending amine consisting of 1,3-diaminopentane; said amine blend having an equivalent weight of between about 40 and 50 and containing a solids content of between about 40 and 60% by weight, and b) an aliphatic polyisocyanate having a viscosity of between 1000-3500 cps at 25.degree. C.; wherein the ratio between isocyanate component equivalents and polyester-polyol/amine component equivalents is between about 1.3:1 to 1.7:1. ### Claim 14 (depends on 13) A substrate according to claim 13 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said modified polyester-polyol is a modified hexaneadipate diol saturated polyester polyol, said trihydric alcohol is an .alpha.,.alpha.,.alpha.-trimethylol alkane having the formula: ##STR5## wherein R is an alkyl group of 1 to 8 carbon atoms and said polyfunctional diol containing a carboxylic acid group is a .alpha.,.alpha.-dimethylol alkanoic acid of the formula: ##STR6## wherein R is an alkyl group of 1 to 8 carbon atoms. ### Claim 15 (depends on 14) A substrate according to claim 14 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said hexaneadipate diol is a 1,4-hexaneadipate diol, said .alpha.,.alpha.,.alpha.-trimethylol alkane is a member selected from the group consisting of trimethylolethane, trimethylolpropane and trimethylolbutane and said .alpha.,.alpha.-dimethylol alkanoic acid is a member selected from the group consisting of 2,2-dimethylol propionic acid, 2,2,-dimethylol butyric acid, 2,2-dimethylol pentanoic acid. ### Claim 16 (depends on 15) A substrate according to claim 15 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said low viscosity polyol is a member selected from the group consisting of polyester-polyols and trihydric polyol modified polyester-polyols having incorporated therein between about 2 and 10% of .alpha.,.alpha.,.alpha.-trimethylolalkane selected from the group consisting of trimethylolethane, trimethylolpropane and trimethylolbutane. ### Claim 17 (depends on 16) A substrate according to claim 16 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said .alpha.,.alpha.,.alpha.-trimethylol alkane is trimethylolethane and said .alpha.,.alpha.-dimethylol alkanoic acid is 2,2-dimethylol propionic acid. ### Claim 18 (depends on 17) A substrate according to claim 17 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said low molecular weight chain extending diol or triol is 1,4-butanediol. ### Claim 19 (depends on 18) A substrate according to claim 18 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said first neutralizing amine is a mixture comprising a major amount of triethanol amine and a minor amount of diethanol amine. ### Claim 20 (depends on 19) A substrate according to claim 19 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said second neutralizing amine is 2-amino-2-methyl-1-propanol. ### Claim 21 (depends on 20) A substrate according to claim 20 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said first neutralizing amine is a mixture comprising about 85% of triethanol amine and 15% of diethanol amine. ### Claim 22 (depends on 21) A substrate according to claim 21 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said non-ionic detergent is a polymeric dispersant with nonionic anchor groups. ### Claim 23 (depends on 22) A substrate according to claim 22 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said first chain extending amine is diethanol amine. ### Claim 24 (depends on 22) A substrate according to claim 22 wherein, in the water based, solvent free, two component polyurethane-polyurea dispersion applied, said second chain extending amine is diethylenetriamine.