# US 5,349,010 A · Water-dispersible polyester resins and process for their preparation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,010 A - Document ID: US5349010A - Status: Granted - Kind: A - Application number: 07/954,857 - Filed: 1992-09-30 - Granted: 1994-09-20 - Earliest claimed: 1992-09-30 - Assignees: Eastman Chemical Company - Inventors: Thauming Kuo - Web page: https://patentgrep.com/patent/US5349010A ## CPC - C08G 63/6884: {derived from polycarboxylic acids and polyhydroxy compounds} - C08G 63/20: Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups - C08G 69/44: Polyester-amides - C09D 167/00: Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain (based on polyester-amides C09D177/12; based on polyester-imides C09D179/08); Coating compositions based on derivatives of such polymers - C09D 177/12: Polyester-amides - 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) ## Abstract Disclosed is a water-dissipatable or dispersible polyester containing sulfonate groups that has improved stability prepared from a monocarboxylic acid sulfomonomer. This polyester can be prepared in a one or two step process but the preferred two step process entails polymerizing the reactants wherein the monocarboxylic acid sulfomonomer has been pre-reacted with a monofunctional reactant containing at least three hydroxyl groups to form a diol adduct. ## Claims ### Claim 1 A water-dispersible composition comprising the polyester made of the moieties of reaction products: (a) at least one difunctional dicarboxylic acid which is not a sulfomonomer; (b) about 1 to 20 mol % of at least one monocarboxylic acid sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing non-metallic sulfonate group attached to an aromatic or cycloaliphatic nucleus; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --C(R.sup.1).sub.2 --OH groups wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R.sup.1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms; (d) about 0 to 40 mol % of difunctional reactant selected from hydroxycarboxylic acids having one --C(R).sub.2 --OH group, aminocarboxylic acids having one --NRH group, amino-alcohols having one --C(R).sub.2 --OH group and one --NRH group, or mixtures of said difunctional reactants wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms; and (e) up to 40 mol % of a multifunctional reactant containing at least three functional groups selected from hydroxyl, carboxyl, and mixtures thereof wherein at least a portion of the multifunctional reactant contains at least three hydroxyl groups, wherein all stated mol percentages are based on the total of all acid, hydroxyl and amino group containing reactants being equal to 200 mol %, and wherein the polymer is no longer acidic, having an acid number less than 20 and contains proportions of acid-group containing reactants (100 mol % acid) to hydroxy- and amino-group containing reactants (100 mol % base) such that the value of EQ (base) divided by EQ (acid) is between about 0.5 and 2. ### Claim 2 (depends on 1) The composition according to claim 1 wherein (e) is about 1 to 40 mol % of a multifunctional reactant containing at least three hydroxyl groups. ### Claim 3 A process for the preparation of a polyester comprising reacting the following reactants under polycondensation conditions: (a) at least one difunctional dicarboxylic acid which is not a sulfomonomer; (b) about 1 to 20 mol % of at least one monocarboxylic acid sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing non-metallic sulfonate group attached to an aromatic or cycloaliphatic nucleus; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --C(R.sup.1).sub.2 --OH groups wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R.sup.1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms; (d) about 0 to 40 mol % of difunctional reactant selected from hydroxycarboxylic acids having one --C(R).sub.2 --OH group, aminocarboxylic acids having one --NRH group, amino-alcohols having one --C(R).sub.2 --OH group and one --NRH group, or mixtures of said difunctional reactants wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms; and (e) up to 40 mol % of a multifunctional reactant containing at least three functional groups selected from hydroxyl, carboxyl, and mixtures thereof wherein at least a portion of the multifunctional reactant contains at least three hydroxyl groups, wherein all stated mol percentages are based on the total of all acid, hydroxyl and amino group containing reactants being equal to 200 mol %, and wherein the polymer is no longer acidic, having an acid number less than 20 and contains proportions of acid-group containing reactants (100 mol % acid) to hydroxy- and amino-group containing reactants (100 mol % base) such that the value of EQ (base) divided by EQ (acid) is between about 0.5 and 2. ### Claim 4 The composition comprising the ester adduct made of the moieties of reaction products: (A) a monocarboxylic acid sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing non-metallic sulfonate group attached to an aromatic or cycloaliphatic nucleus, and (B) a multifunctional reactant containing at least three hydroxyl groups. ### Claim 5 A water-dispersible composition comprising the polyester made of the moieties of reaction products: (a) at least one difunctional dicarboxylic acid which is not a sulfomonomer; (b) about 1 to 20 mol % of at least one diol that is a diol adduct of a multifunctional reactant containing at least three hydroxyl groups and a monocarboxylic acid sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing non-metallic sulfonate group attached to an aromatic or cyclo-aliphatic nucleus; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --C(R.sup.1).sub.2 --OH groups wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R.sup.1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms; (d) about 0 to 40 mol % of difunctional reactant selected from hydroxycarboxylic acids having one --C(R).sub.2 --OH group, aminocarboxylic acids having one --NRH group, amino-alcohols having one --C(R).sub.2 --OH group and one --NRH group, or mixtures of said difunctional reactants wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms; and (e) about 0 to 40 mol % of a multifunctional reactant containing at least three functional groups selected from hydroxyl, carboxyl, and mixtures thereof, wherein all stated mol percentages are based on the total of all acid, hydroxyl and amino group containing reactants being equal to 200 mol %, and wherein the polymer is no longer acidic, having an acid number less than 20 and contains proportions of acid-group containing reactants (100 mol % acid) to hydroxy- and amino-group containing reactants (100 mol % base) such that the value of EQ (base) divided by EQ (acid) is between about 0.5 and 2. ### Claim 6 (depends on 5) The composition of claim 5 wherein reactant (b) is selected from the diol adduct prepared from a monocarboxylic acid sulfomonomer of the following: ##STR2## wherein M is Na.sup.+, K.sup.+, or NH.sub.4.sup.+ and X is O, S, CH.sub.2, or SO.sub.2. ### Claim 7 (depends on 6) The composition of claim 6 wherein said monocarboxylic acid sulfomonomer is 3-sodiosulfobenzoic acid. ### Claim 8 (depends on 5) The composition of claim 5 wherein reactant (c) is selected from residues of neopentyl glycol, cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalyl hydroxypivalate, 2,2,4-trimethyl-1,3-pentanediol, and 2-methyl-1,3-propanediol. ### Claim 9 (depends on 8) The composition of claim 8 wherein reactant (c) is neopentyl glycol. ### Claim 10 (depends on 5) The composition of claim 5 wherein reactant (e) is selected from residues of trimethylolpropane, trimethylolethane, glycerol, 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,3,4-tetrahydroxy-butane, 1,2,3,4,5-pentahydroxypentane, and 1,2,3,4,5,6-hexahydroxyhexane. ### Claim 11 (depends on 10) The composition of claim 10 wherein reactant (e) is trimethylolpropane. ### Claim 12 (depends on 5) The composition of claim 5 wherein reactants (a) are isophthalic acid and adipic acid. ### Claim 13 (depends on 5) The composition of claim 5 wherein the moiety from reactant (a) is between about 20 to 100 mol % of an aromatic dicarboxylic acid and about 10 to 80 mol % of an aliphatic dicarboxylic acid; the moiety from reactant (b) is present in a concentration of about 1 to about 20 mol%; the moiety from reactant (c) is present in a concentration-of at least 60 mol %; and the moiety from reactant (e) is present in a concentration of about 1 to 40 mol %. ### Claim 14 (depends on 13) The composition of claim 13 wherein the moiety from reactant (a) is between about 40 to 70 mol % of an aromatic dicarboxylic acid and about 10 to 60 mol % of an aliphatic dicarboxylic acid; the moiety from reactant (b) is present in a concentration of about 2 to about 12 mol%; the moiety from reactant (c) is present in a concentration of at least 70 mol %; and the moiety from reactant (e) is present in a concentration of about 10 to 20 mol %. ### Claim 15 (depends on 14) The composition of claim 14 wherein the moiety from reactant (a) is between about 55 to 60 mol % of an aromatic dicarboxylic acid and about 35 to 45 mol % of an aliphatic dicarboxylic acid; the moiety from reactant (b) is present in a concentration of about 3.5 to 4.5 mol %, the moiety from reactant (c) is present in a concentration of at least 80 mol %, and the moiety from reactant (e) is present in a concentration of about 14 to 18 mol % and wherein the acid number of the polyester is less than 10. ### Claim 16 (depends on 5) A coating composition comprising: (A) 15 to 45 percent, based on the weight of the total coating composition, of the polyester of claim 5, (B) 30 to 80 percent, based on the weight of the total coating composition, of water, (C) 0 to 30 percent, based on the total weight of the coating composition, of a suitable organic solvent, and (D) 0 to 40 weight percent of a crosslinking agent, based on the weight of the polyester and the crosslinking agent. ### Claim 17 (depends on 16) The coating composition according to claim 16 wherein the amount of component (A) is 20 to 40 percent, the amount of component (B) is 60 to 75 percent, the amount of component (C) is 3 to 10 percent, and the amount of component (D) is 20 to 35 percent. ### Claim 18 (depends on 17) The coating composition according to claim 17 wherein said coating composition contains at least one pigment. ### Claim 19 (depends on 18) The coating composition according to claim 18 wherein said coating composition further contains at least one pigment dispersing additive. ### Claim 20 (depends on 19) The coating composition according to claim 19 wherein said pigment dispersing additive is selected from Disperbyk-181, Disperbyk, Disperbyk 101, BYK-P104S available from BYK-Chemie USA, and Dow-Corning 14 additive. ### Claim 21 (depends on 5) A shaped or formed article coated with the cured enamel composition according to claim 5. ### Claim 22 (depends on 16) A coated substrate comprising the coating composition according to claim 16 coated onto a substrate. ### Claim 23 (depends on 22) The coated substrate of claim 22 wherein said substrate is paper, polyethylene, polypropylene, polyester, aluminum, steel, glass, or a urethane elastomer. ### Claim 24 A process for the preparation of a polyester comprising (I) reacting in the presence of a catalytic amount of a catalyst, a multifunctional reactant containing at least three hydroxyl groups and (b) a monocarboxylic acid sulfomonomer containing at least one metallic sulfonate group or nitrogen-containing non-metallic sulfonate group attached to an aromatic or cycloaliphatic nucleus, under conditions such that substantially all of the acid functionalty of said monocarboxylic acid sulfomomoner is esterified and an intermediate reaction product is formed; (II) reacting the resultant intermediate reaction product with the following reactants; (a) at least one difunctional dicarboxylic acid which is not a sulfomonomer; (c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --C(R.sup.1).sub.2 --OH groups wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R.sup.1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms; (d) about 0 to 40 mol % of difunctional reactant selected from hydroxycarboxylic acids having one --C(R).sub.2 --OH group, aminocarboxylic acids having one --NRH group, amino-alcohols having one --C(R).sub.2 --OH group and one --NRH group, or mixtures of said difunctional reactants wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms; and (e) 0 to 40 mol % of a multifunctional reactant containing at least three functional groups selected from hydroxyl, carboxyl, and mixtures thereof, wherein all stated mol percentages are based on the total of all acid, hydroxyl and amino group containing reactants being equal to 200 mol %, and wherein the polymer contains proportions of acid-group containing reactants (100 mol % acid) to hydroxy- and amino-group containing reactants (100 mol % base) such that the value of EQ (base) divided by EQ (acid) is between about 0.5 and 2. ### Claim 25 (depends on 24) The process according to claim 24 wherein said multifunctional reactant containing at least three hydroxyl groups is present in molar excess to said monocarboxylic acid sulfomonomer.