Solvent-borne thermosetting polyamide urethane and / or urea-based coatings

Abstract

The present invention relates to thermosetting polymer solutions, such as polyurethanes and / or polyureas, containing sufficient polyamide to provide the strength, adhesion, and durability of polyamides, which can be formulated as one- or two-component solvent-based coating compositions. The polyamides provide thermosets that are harder, more chemically resistant, and often tougher than similar polyamide-rich water-based polyurethanes. The compositions of the present disclosure differ from other polyamides because they are formulated to a viscosity suitable for use as a coating and then crosslinked to form a hard thermoset film.

Description

[Technical Field]

[0001] The present invention relates to polymer systems based on hydroxyl-, amine-, or carboxylic acid-terminated polyamide-rich oligomers that are reacted with polyisocyanates (optionally blocked) or polyepoxides to make thermosetting solvent-based ink and coating compositions. These can be one- or two-component systems. [Background technology]

[0002] Due to the hydrogen bonding associated with the amide linkages, polyamides are typically processed in the melt stage or, in the case of some very stiff aromatic polyamide chains, through a process that orients the chains during processing. Polyamides can have very high strength and excellent barrier properties. WO 2014 / 126739 and WO 2014 / 126741, filed by the same applicant, disclose telechelic N-alkylated polyamide polymers and the use of those telechelic polyamides in aqueous polyamide-urea dispersions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2014 / 126739 [Patent Document 2] International Publication No. 2014 / 126741 Summary of the Invention [Means for solving the problem]

[0004] One objective was to create a new and improved polyamide-rich crosslinkable (thermosetting) polymer system that could be used in coating compositions with higher performance levels than the previous WO 2014 / 126741 publication, which was based on water-based polyamides. Water-based systems inherently suffer from the problem of surfactant moieties included to facilitate the formation of water-based dispersions. The surfactant species tend to bond to the final coating at the interfaces where individual particles of the polyamide dispersion attempt to fuse into a coherent barrier film. To some extent, the surfactant-rich phase in the final coating can reduce the final film strength and result in easier penetration of water and other polar species through the final film. Annealing the coating from the water-based dispersion can better fuse the individual particles and promote migration of the surfactant species away from the interparticle interfaces.

[0005] If solvent-borne polyamide-rich compositions could be developed using small amounts of solvent and / or solvents acceptable to the coatings industry, these solvent-borne compositions would be expected to have improved mechanical and barrier properties compared to aqueous polymer dispersions. However, creating solvent-borne polyamide-rich compositions for coatings or inks presents several inherent challenges. First, many common solvents are not suitable for polyamides. Due to hydrogen bonding, polyamides tend to become solid at room temperature and up to approximately 130°C. Solvents suitable for coatings generally evaporate rapidly at or slightly above 15°C, so heating is not required to convert the coating from a wet film to a dry film when using these solvents. However, these solvents are difficult to incorporate into polyamides at temperatures above 100°C. As the molecular weight of polyamides increases, their compatibility with solvents decreases.

[0006] Another objective is to prepare crosslinked polyamide-rich coatings for a variety of substrates from liquid polymer compositions at room temperature (e.g., 20-25°C, preferably 24°C) while minimizing the use or release of harmful organic solvents (using the minimum amount of organic solvents and those most accepted by the coatings industry and least hazardous).

[0007] Dicarboxylic acids are preferred for forming polyamides having 4 to 50 (and sometimes 10 to 50) carbon atoms, as they have been found to provide more processable polyamides. Examples of dicarboxylic acids include sebacic acid and dimer fatty acids. The inventors have found it desirable to have diamines with either secondary amine end groups and / or a contorted structure in which the two nitrogen atoms (from the diamine component) that form the amide bond of the polyamide are relatively rigidly positioned, often preventing effective or strong hydrogen bonding of the amide bond of the polyamide, or diamines with sterically bulky substituents on the carbon atom adjacent to the primary nitrogen group, which can prevent the nitrogen or amide bond from forming strong hydrogen bonds with other amide bonds in the polyamide phase. Such diamines, which disrupt hydrogen bonds near the amide bond, make the resulting polyamide more processable as a melt and as a solvent-based composition. Such diamines can be selected from cyclic diamines, such as piperazine, 4,4'-trimethylenepiperidine, certain phenylene diamines, and certain diphenylmethylene diamines. It was unexpected that flexibility in the diamine component and a single hydrocarbon chain, double hydrocarbon chains, or rings between the carboxylic acid moieties would be more desirable to achieve a polyamide that can be processed at temperatures at or slightly above 25°C.

[0008] The inventors have developed a method for increasing the molecular weight of the polyamide-rich polymer of the composition and crosslinking the composition into a thermoset. The inventors have also developed a method for incorporating other softer and softer polymer segments into the composition to facilitate rendering the otherwise hard and waxy polyamide solvent swellable into a liquid coating composition with a viscosity suitable for application as a coating.

[0009] The problem of solvent volatility is partially solved by using solvent blends, if necessary, to allow heating to temperatures where the polyamide and solvent can be blended. Solvent volatility is partially controlled by using very polymer-rich compositions. Solvent-swellable polyamide-rich compositions are formulated with polymeric solids to minimize solvent recovery during film formation and solvent release to the environment.

[0010] The following embodiments of the present subject matter are contemplated.

[0011] 1. A thermosetting composition comprising: a) 10 to 75 wt. % polyamide oligomer having predominantly at least two amide bonds and two end groups selected from amine end groups, hydroxyl end groups, or carboxylic acid end groups; b) 10 to about 40 or 50 weight percent of a diisocyanate or polyisocyanate component (optionally where the isocyanate reactivity is temporarily blocked) that reacts with amine, carboxyl, and / or hydroxyl groups to form covalent chemical bonds; c) optionally one or more non-reactive organic diluents; d) up to 50, more preferably up to 40 or 25 wt. % of one or more compounds (not polyamides) having a molecular weight of less than 500 g / mole and having three or more groups reactive with isocyanates selected from the group of amine groups and hydroxyl groups; the thermosetting composition of a), b), c), and d) prior to reaction of the end groups selected from amine end groups, hydroxyl end groups, or carboxylic acid end groups with the isocyanate groups, has an average functionality of all of the isocyanate end groups, amine end groups, hydroxyl end groups, and carboxylic acid end groups per molecule of 2.1 or greater; The weight percentages are based on the total components of the thermosetting composition; The thermosetting composition includes a composition, wherein the composition, prior to reaction with the diisocyanate or polyisocyanate, when at a solids content of 50% or diluted to 50%, has a viscosity of less than 10,000 cps (more desirably less than 5,000 cps or 2,000 cps, preferably about 100 to 5,000 cps) at 25°C, as measured with a Brookfield rotating disc viscometer at 5 rpm and using a #6 spindle.

[0012] 2. The polyamide oligomer is a) a diamine having two amine groups capable of forming a covalent bond with the carbonyl of a carboxylic acid selected from the group consisting of diamines having 4 to 60 carbon atoms (optionally including one other heteroatom) with two secondary terminal amine groups and / or diamines having 4 to 60 carbon atoms (optionally including one other heteroatom) with one or two primary amine groups (desirably, the diamine having one or two primary amine groups is characterized as a) a diamine in which a substituent on the carbon atom adjacent to the primary amine nitrogen blocks the nitrogen from forming a strong hydrogen bond with a nearby amide bond and / or the primary amine nitrogen is pendant from an aliphatic or aromatic ring structure at a position from the ring such that it cannot form a strong hydrogen bond with a nearby amide bond); b) polyamide repeat units derived from polymerizing lactone and / or carboxylic acid monomers, the lactone or carboxylic acid units being derived from an acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids of 4 to 50 carbon atoms, the lactone and / or carboxylic acid monomers forming the repeat units such that the carbonyl from the lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid reacts with a primary or secondary amine nitrogen to form an amide bond, thereby forming a polyamide oligomer.

[0013] 3. The thermosetting composition of embodiment 2, wherein at least 40, desirably at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are cyclic diamines having 4 to 15 (more desirably 4 to 13) carbon atoms, such as piperazine and 4,4'-trimethylethylenedipiperidine, in which the nitrogen atoms are in secondary amine groups and part of one or more rings.

[0014] 4. The thermosetting composition of embodiment 2 or embodiment 3, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamine is a diamine having two primary amine groups, and the predominant diamine having two primary amine groups has the following structure: [ka]

[0015] 5. The thermosetting composition of any one of embodiments 2 to 4, wherein the polyamide oligomer is comprised of repeat units from a dicarboxylic acid reacted with an amine group, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the dicarboxylic acid moieties in the amide repeat units are dicarboxylic acids of 10 to 50 carbon atoms, more desirably 25 to 50 carbon atoms.

[0016] 6. The thermosetting composition of any one of embodiments 2 to 5, wherein at least 50 wt. % (more desirably at least 60, 70, 80, or 90 wt. %) of the repeat units from carboxylic acid are derived from optionally hydrogenated dimer fatty acid.

[0017] 7. The thermosetting composition of the previous embodiments 2 to 6, wherein the combined repeat units of diamine and lactone and / or carboxylic acid monomers, which form at least one amide bond during their polymerization into the polyamide, are 20 to about 60 weight percent of the thermosetting composition.

[0018] 8. The thermosetting composition of any one of embodiments 2 to 7, wherein the combined repeat units of diamine and lactone and / or carboxylic acid monomers that form at least one amide bond during their polymerization into said polyamide are 25 to about 50 weight percent of the thermosetting composition.

[0019] 9. The thermosetting composition of any one of embodiments 2 to 8, wherein at least 90% by weight of the repeat units from the diamine are derived from cyclic and / or bicyclic diamines of 4 to 15 (more desirably 4 to 13) carbon atoms, and wherein the nitrogen atom of the diamine is part of a cyclic structure, such as piperazine or 4,4'-trimethylenepiperidine.

[0020] 10. The thermosetting composition of any one of the preceding embodiments, wherein the reactive polyisocyanate or the blocked isocyanate, when both are present, in combination, is present in solution in an amount of about 10 to 50 weight percent of the solution (based on the weight of all components of the composition).

[0021] 11. The thermosetting composition of any one of embodiments 1 to 10, wherein the organic diluent is present in an amount of from about 10 to about 50 weight percent of the composition.

[0022] 12. The thermosetting composition of embodiment 11, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate.

[0023] 13. The thermosetting composition of any one of the preceding embodiments, wherein the solution after evaporation of the solvent is thermosetting.

[0024] 14. The thermosetting composition of any one of embodiments 1 to 13, or 15 to 16 (below), formed into a free-standing film, coating, or adhesive.

[0025] 15. The thermosetting composition of any one of the preceding embodiments, wherein the polyisocyanate component has two or more isocyanate groups per polyisocyanate, and the ratio of isocyanate groups to combined hydroxyl, amino, and / or carboxyl groups of the polyisocyanate is from 2:1 to 1:1.

[0026] 16. The thermosetting composition of any one of embodiments 1 to 13 or 15, wherein as the organic diluent evaporates, the polyamide oligomer is crosslinked via reaction with the polyisocyanate component reacting with hydroxyl, carboxyl, and / or amino groups to form covalent chemical bonds, producing a polymer of number average molecular weight of at least 1,000,000 g / mole.

[0027] 17. A method for forming a thermosetting coating or film, comprising: a) polymerizing a diamine having 4 to 60 carbon atoms (optionally including one other heteroatom) and selected from the group consisting of a diamine having two secondary terminal amine groups and a diamine having two primary amine groups, wherein the diamine having two primary amine groups is preferably of the following structure: [ka] reacting with carboxylic acid groups, wherein the carboxylic acid units are from lactone and / or carboxylic acid components selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids of 4 to 50 carbon atoms, to form repeat units with a carbonyl or nitrogen as part of an amide bond, thereby forming a polyamide oligomer, wherein the polyamide oligomer has at least two end groups selected from an amine group, a carboxyl group, or a hydroxyl group; b) optionally heating the polyamide oligomer to a temperature of 100-150°C to make it a more processable liquid; c) adding one or more non-reactive organic diluents; d) adding to the polyamide oligomer about 10 to about 40 weight percent of a polyisocyanate component (optionally having a blocked isocyanate group) that reacts with the hydroxyl, carboxyl, and / or amino groups to form a covalent chemical bond with the nitrogen of the amino group or the oxygen of the hydroxyl group, or reacts with the carboxyl groups and isocyanate, hydroxyl, or amine groups, wherein the weight percent of diamine and carboxylic acid repeat units in the solution is about 10 to about 75 weight percent. % by weight, the amount of organic diluent is up to 50% by weight of the solution, the amount of the component reactive with hydroxyl groups, carboxyl groups, and / or amino groups is about 10 to about 40% by weight of the solution, and the solution at 50% solids prior to reaction with the polyisocyanate has a viscosity of less than 10,000 cps (more desirably less than 2,000 cps, preferably less than 500 cps) at 25°C as measured by a Brookfield rotating disk viscometer at 5 rpm and using a #6 spindle.

[0028] 18. The method of embodiment 17, wherein the organic diluent is evaporated from the solution and the isocyanate groups react with the hydroxyl, carboxyl, and / or amino groups to form covalent bonds.

[0029] 19. The method of embodiment 18, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are cyclic diamines in which the nitrogen atoms are secondary and part of a ring and have 4 to 15 (more desirably 4 to 13) carbon atoms, such as piperazine and 4,4'-trimethylethylenedipiperidine.

[0030] 20. The method of embodiment 18, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are diamines having two primary amine groups, and the predominant diamines having two primary amine groups have the following structure: [ka]

[0031] 21. The method of any one of embodiments 17 to 20, wherein at least 50 wt.% (more desirably at least 60, 70, 80, or 90 wt.%) of the repeat units from carboxylic acids are derived from dicarboxylic acids of 10 to 50 carbon atoms, more desirably 25 to 50 carbon atoms.

[0032] 22. The method of embodiment 21, wherein at least 50% by weight (more desirably at least 60, 70, 80, or 90% by weight) of the repeat units from carboxylic acid are derived from optionally hydrogenated dimer fatty acid.

[0033] 23. The method of any one of embodiments 17 to 20, wherein the component that reacts with hydroxyl groups, carboxyl groups, and / or amino groups is a blocked polyisocyanate having two or more isocyanate groups in chemically blocked form that can be deblocked by thermal heating, and the blocked isocyanate groups can be added to the polyamide oligomer without chemical reaction until the blocked polyisocyanate is unblocked.

[0034] 24. The method of any one of embodiments 17 to 23, further comprising the process step of adding to the composition up to 25% by weight of one or more compounds (not polyamides) having a molecular weight of less than 500 g / mol and having three or more groups reactive with isocyanates selected from the group of amine groups, carboxyl groups, and hydroxyl groups, to promote crosslinking of the final composition.

[0035] 25. The method of embodiment 17, wherein the polyisocyanate is not added until the composition is ready to form a coating or film, and wherein the polyisocyanate begins to react with the polyamide oligomer via its isocyanate groups upon addition of the polyisocyanate to the polyamide oligomer.

[0036] 26. A thermosetting composition comprising: a) 10 to 75 wt. % of a polyamide oligomer having mainly two end groups selected from an amine end group, a carboxy end group, and a hydroxyl end group; b) 10 to about 40 weight percent of a component having two or more reactive oxirane rings (epoxy groups) that react with amine groups, carboxyl groups, and / or hydroxyl groups to form covalent chemical bonds; wherein the composition, prior to reaction of the component having two or more reactive oxirane rings, when at 50% solids or diluted to 50%, has a viscosity of less than 10,000 cps (more desirably less than 5,000 cps, preferably about 100-5,000 cps) at 25°C as measured on a Brookfield rotating disk viscometer using a rotation speed of 5 rpm (revolutions per minute) and a #6 spindle; c) optionally one or more non-reactive organic diluents; d) up to 25% by weight of one or more compounds (not polyamides) having a molecular weight of less than 500 g / mole and having three or more groups reactive with the component having two or more reactive oxirane rings selected from amine groups, carboxyl groups, and hydroxyl groups; the thermosetting composition of a), b), c), and d) prior to reaction of the end groups selected from amine, carboxyl, and hydroxyl end groups with the component having two or more reactive oxirane rings has an average functionality of all oxirane rings or less per molecule relative to the combined amine, carboxyl, and hydroxyl groups of 2.1 or more; The weight percentages are based on the total components for the thermosetting composition.

[0037] 27. A polyamide oligomer, a) a diamine having two amine groups capable of forming a covalent bond with the carbonyl of a carboxylic acid selected from the group consisting of diamines having 4 to 60 carbon atoms (optionally including one other heteroatom) with two secondary terminal amine groups and / or diamines having 4 to 60 carbon atoms (optionally including one other heteroatom) with one or two primary amine groups, wherein the diamine having one or two primary amine groups is characterized as a) a diamine in which a substituent on the carbon atom adjacent to the primary amine nitrogen blocks the nitrogen from forming a strong hydrogen bond with a nearby amide bond and / or the primary amine nitrogen is pendant from an aliphatic or aromatic ring structure at a position from the ring such that it cannot form a strong hydrogen bond with a nearby amide bond; 27. The thermosetting composition of embodiment 26, wherein the polyamide repeat units are derived from the polymerization of lactone and / or carboxylic acid monomers, the lactone or carboxylic acid units being derived from an acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids of 4 to 50 carbon atoms, and the lactone and / or carboxylic acid monomers form the repeat units such that the carbonyl from the lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid reacts with a primary or secondary amine nitrogen to form an amide bond, thereby forming a polyamide oligomer.

[0038] 28. The thermosetting composition of embodiment 27, wherein at least 40, desirably at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are cyclic diamines in which the nitrogen atoms are secondary and are part of one or more rings and have 4 to 15 (more desirably 4 to 13) carbon atoms, such as piperazine and 4,4'-trimethylethylenedipiperidine.

[0039] 29. The thermosetting composition of embodiment 27, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are diamines having two primary amine groups, and the predominant diamines having two primary amine groups have the following structure: [ka]

[0040] 30. The thermosetting composition of any one of embodiments 27 to 29, wherein the polyamide oligomer is comprised of repeat units from a dicarboxylic acid reacted with an amine group, and wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the dicarboxylic acid components are dicarboxylic acids of 10 to 50 carbon atoms.

[0041] 31. The thermosetting composition of any one of embodiments 27 to 30, wherein at least 50 wt. % (more desirably at least 60, 70, 80, or 90 wt. %) of the repeat units from carboxylic acid are derived from optionally hydrogenated dimer fatty acid.

[0042] 32. The thermosetting composition of any one of embodiments 27 to 30, wherein the combined repeat units of the diamine and acid monomer that form at least one amide bond during polymerization into the polyamide are 20 to about 60 weight percent of the thermosetting composition.

[0043] 33. The thermosetting composition of any one of embodiments 27 to 30, wherein the combined repeat units of the diamine and acid monomer that form at least one amide bond during polymerization into the polyamide are 25 to about 50 weight percent of the thermosetting composition.

[0044] 34. The thermosetting composition of any one of embodiments 27 to 30, wherein at least 90% by weight of the repeat units from the diamine are derived from cyclic diamines of 4 to 15 (more desirably 4 to 13) carbon atoms, and wherein the nitrogen atom of the diamine is part of a cyclic structure, such as piperazine or 4,4'-trimethylenepiperidine.

[0045] 35. The thermosetting composition of any one of embodiments 27 to 30, wherein the organic diluent is present in an amount of from about 10 to about 50 weight percent of the composition.

[0046] 36. The thermosetting composition of any one of embodiments 27 to 30, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate.

[0047] 37. The thermosetting composition of any one of embodiments 26 to 30, wherein when the solution forms a film or coating by evaporation of the organic diluent, the polyamide oligomer is crosslinked via reaction with said component having two or more oxirane rings that react with reactive groups selected from hydroxyl, carboxylic acid, and amino groups to form covalent chemical bonds, producing a polymer of number average molecular weight of at least 1,000,000 g / mol.

[0048] 38. A method for forming a thermosetting coating or film, comprising: a) polymerizing a diamine having from 4 to 60 carbon atoms (optionally including one other heteroatom) and selected from the group consisting of a diamine having two secondary terminal amine groups and a diamine having two primary amine groups, preferably the diamine having the predominant two primary amine groups has the structure: [ka] reacting with carboxylic acid groups, wherein the carboxylic acid units are from lactone and / or carboxylic acid components selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids of 4 to 50 carbon atoms, to form repeat units with a carbonyl or nitrogen as part of an amide bond, thereby forming a polyamide oligomer, wherein the polyamide oligomer has at least two end groups selected from an amine group, a carboxyl group, and a hydroxyl group; b) optionally heating the polyamide oligomer to a temperature of 100-150°C to make it a more processable liquid; c) adding one or more non-reactive organic diluents; d) adding to the polyamide oligomer from about 10 to about 40 weight percent of a component having two or more reactive oxirane rings that react with a hydroxyl, carboxy, or amino group to form a covalent chemical bond with the nitrogen of the amino group, the carboxyl of the carboxyl group, or the oxygen of the hydroxyl group, to form a pourable solution at 25°C, wherein the weight percent of diamine and carboxylic acid repeat units in the solution is from about 10 to about 75 weight percent, and the amount of organic diluent is up to 50 weight percent of the solution, the amount of the component having two or more reactive oxirane rings that react with hydroxyl groups, carboxyl groups, and / or amino groups is about 10 to about 40% by weight of the solution, and the solution at 50% solids prior to reaction of the component having two or more reactive oxirane rings has a viscosity of less than 10,000 cps (more desirably less than 2,000 cps, preferably less than 500 cps) at 25°C as measured by a Brookfield rotating disk viscometer at 5 rpm using a #6 spindle.

[0049] 39. The method of embodiment 38, wherein the organic diluent is evaporated from the solution and the component having two or more reactive oxirane rings reacts with the hydroxyl group, carboxylic acid group, and / or amino group to form a covalent bond.

[0050] 40. The method of embodiment 38, wherein at least 50, more desirably at least 80, and preferably at least 90 mol % of the diamines are cyclic and / or bicyclic diamines, such as piperazine or 4,4'-trimethylenedipiperidine, in which the nitrogen atom is a secondary nitrogen group, is part of a ring, and has 4 to 15 (more desirably 4 to 13) carbon atoms.

[0051] 41. The method of embodiment 38, wherein at least 50, more desirably at least 80, and preferably at least 90 mole percent of the diamines are diamines having two primary amine groups, and desirably the predominant diamines having two primary amine groups have the following structure: [ka]

[0052] 42. The method of embodiment 38, wherein at least 50% by weight (more desirably at least 60, 70, 80, or 90% by weight) of the repeat units from carboxylic acids are derived from dicarboxylic acids of 10 to 50 carbon atoms, more desirably 25 to 50 carbon atoms.

[0053] 43. The method of embodiment 38, wherein at least 50% by weight (more desirably at least 60, 70, 80, or 90% by weight) of the repeat units from carboxylic acid are derived from optionally hydrogenated dimer fatty acid.

[0054] 44. The method of embodiment 38, further comprising the process step of adding to the composition up to 25 wt. % of one or more compounds (not polyamides) of molecular weight less than 500 g / mol having three or more groups that react with components having two or more reactive oxirane rings to promote crosslinking of the final composition. DETAILED DESCRIPTION OF THE INVENTION

[0055] Thermosetting films or thermosetting polymer solutions with a high percentage of polyamide segments have been disclosed for various applications where the strength and / or chemical resistance of polymers with polyether, polyester, or polycarbonate segments are insufficient. These solutions are useful because the polyamide is formulated to be sufficiently flexible at its molecular weight to form a pourable solution from a beaker at 20-50°C, containing more than 30, 40, 50, 60, 70, or 80% solids by weight of the polymer component (the polymer component is defined as the nonvolatile or polymer-forming component) and a complementary amount of volatile solvent (100% by weight or the amount of nonvolatile component needed to make up the total).

[0056] The first advantage of this technology is that it allows for thermosetting compositions with a high polyamide content. Amide bonds, especially in thermosetting compositions, provide good resistance to deformation, UV rays, moisture, etc. Development of thermosetting polyamides has been difficult because conventional polyamides require relatively high temperatures for processing due to intermolecular hydrogen bonding, excluding other polymers and solvents. The use of low-molecular-weight polyamides can improve solvent interaction and promote compatibility with other polymers.

[0057] The first part of the present invention (glass transition temperature (T g A second advantage of replacing low-carbon polyamide segments with polyether or polyester segments is that the polyamide segments tend to promote better wetting and adhesion to various polar substrates, such as glass, nylon, and metal, compared to polyester- or polyether-based polyurethanes. The hydrophobicity / hydrophilicity of the polyamide can be adjusted by varying the ratio of hydrocarbyl moieties to amide bonds in the polyamide. Diacids, diamines, aminocarboxylic acids, and lactones with a high carbon-to-nitrogen ratio tend to be hydrophobic. As the carbon-to-nitrogen ratio of the polyamide decreases, the polyamide becomes more hydrophilic.

[0058] Therefore, polymers made from polyamide segments can have excellent solvent resistance. Solvent resistance is desirable for coatings or inks. Solvents can deform and stress polymers by swelling, causing premature failure of the polymer or parts made from it. Solvents can cause coatings to swell and delaminate from the substrate at the interface between the two. Adding polyamide to a polymer can improve adhesion to substrates with similar or compatible polar surfaces to the polyamide.

[0059] One objective of this patent application is to utilize a high percentage of amide linkages in polymer segments incorporated into thermosetting copolymers via reaction with polyisocyanates or compounds containing two or more oxirane rings, potentially providing elastomeric properties and resistance to hydrolytic and UV-activated chain scission. In some embodiments, some of the linkages between repeating units may be other than amide linkages. In some embodiments, the linkages between the polyamide oligomer and the isocyanate groups of the polyisocyanate comprise a significant proportion of urea linkages. Urea linkages have a higher melting temperature than urethane linkages, thus tending to allow for higher use temperatures. Some embodiments may allow for urethane linkages between the polyamide oligomer and the isocyanate groups of the polyisocyanate component when preventing chain scission is not a top priority.

[0060] low T gThe key changes from conventional polyamides to obtain polyamide soft segments are the use of one or more of the following: 1) diamine monomers with secondary amine end groups; 2) diamines with cyclic rings where steric factors prevent close packing of amide bonds and strong hydrogen bonding; and 3) diamines with one or two primary amine groups, characterized as: a) diamines in which a substituent on the carbon atom adjacent to the primary amine nitrogen blocks the amide nitrogen from forming strong hydrogen bonds with nearby amide bonds. The amide bond formed between a secondary amine and a carboxylic acid-type group is called a tertiary amide bond. Primary amines react with carboxylic acid-type groups to form secondary amides. The nitrogen atom of secondary amides contains a hydrogen atom, which, in the absence of certain steric hindrance, often hydrogen bonds with the carbonyl group of nearby amides. Intramolecular hydrogen bonding induces high-melting crystallinity and acts as a crosslink, reducing chain mobility. When a tertiary amide group is used, the hydrogen on the nitrogen of the amide bond is removed along with the hydrogen bond. Compared to a secondary amide group with only one hydrogen bond, a tertiary amide bond with one additional alkyl group reduces polar interactions with nearby amide groups when the polymer is present in a bulk polymer sample. This reduced polar interaction means that glassy or crystalline phases containing amide bonds generally melt at lower temperatures than similar amide groups with secondary amide groups. One method for obtaining secondary amine reactants, precursors to tertiary amide bonds, is to replace the nitrogen atom of an amine-containing monomer with an alkyl group. Another method for obtaining secondary amine reactants is to use heterocyclic molecules in which the amine nitrogen is part of a ring structure. Piperazine is a common cyclic diamine in which both nitrogens are secondary and part of a heterocyclic ring.

[0061] The crosslinkable or thermosetting compositions of the present disclosure are desirable because they have a high weight percent of polyamide repeat units in the polyamide oligomer, an adequate amount of a component (often a polyisocyanate or an epoxy compound of the type having two or more oxirane rings capable of reacting with Zerewitinoff groups) that can chemically react with the end groups of the polyamide oligomer to form a thermosetting composition, and, if necessary, a sufficient amount of solvent to reduce the viscosity of the thermosetting composition to a pourable composition at 20-30°C and a solvent that can form a coating or film at 20, 25, or 30°C without undue difficulty.

[0062] In one embodiment, the amide-type repeat units include diamines (the amine end groups react with carboxylic acids to form amide bonds, as described below, and the carboxylic acid components react with amines to form amides.) While the polyamide oligomer may contain other repeat units besides amide-type repeat units, it is contemplated to use a majority of the amide-forming repeat units in the polyamide oligomer.

[0063] The amount of amide-forming repeating units in the thermosetting composition (including solvent, if present) is about 10 or 15 to about 75 wt %, more desirably about 15 or 20 to about 60 wt %, and preferably about 15, 20, or 25 to about 50 wt % of the thermosetting composition. The amount of components reactive with the polyamide oligomer (often polyisocyanates, and sometimes blocked isocyanate compounds) is about 10 to about 50 wt %, more desirably about 10 to about 40 wt %, and preferably about 15 to about 35 wt % of the thermosetting composition. The amount of solvent is desirably up to 60 wt % of the thermosetting composition, more desirably 10 to 60 wt %, more desirably 10 to 50 wt %, and preferably about 10 to 30 wt % of the composition. A low molecular weight component that is difunctional, trifunctional, or higher (preferably trifunctional or higher, which may be present in up to 15 wt % of the thermosetting composition) is optionally present. The thermosetting compositions may also contain conventional amounts of pigments, conventional amounts of additives, fillers, biocides, film enhancers, film surface modifiers (e.g., gloss reducers), and other ingredients conventionally used in coatings, inks, and films.

[0064] Due to the need for thermosetting resins, polyamides typically have reactive end groups at both ends. The reactive groups may be Zerewitinoff groups, such as hydroxyl and / or amine groups. In some embodiments, polyamides may also be terminated with carboxylic acids. Carboxylic acids can react directly with polyepoxides to form high molecular weight reaction products (polyepoxide-extended chains). Carboxylic acid-terminated polyamides can facilitate the decomposition of isocyanate groups (from the polyisocyanate component) to release one molecule of CO and an amine group (the well-known reaction of an isocyanate group with a carboxylic acid group). The amine generated from the isocyanate group can then react with carboxylic acid groups or additional isocyanate groups (if present) on the polyamide. The overall result is that carboxylic acid-terminated polyamides can be reacted to form high molecular weight or crosslinked reaction products. In preferred embodiments, the polyamide end groups are amine or hydroxyl end groups, since this avoids CO generation. Amine (primary or secondary) end groups can be achieved by using a molar excess of the diamine component compared to the carboxylic acid component in producing the polyamide. Hydroxyl end groups can be introduced in a variety of ways. One method is to first form an amine-terminated polyamide and then react the polyamide with a hydroxyl carboxylic acid of 3 to 30 carbon atoms or a lactone of 2 to 10 (or 4 to 10) carbon atoms. When the molar amount of carboxyl functionality in the hydroxyl carboxylic acid and / or lactone is equal to the number of terminal amine groups, a single unit is obtained from the hydroxyl carboxylic acid or lactone. When a molar excess of the hydroxyl carboxylic acid and / or lactone is used, short polyester segments form as part of the polyamide. It is also possible to convert the carboxylic acid groups to hydroxyl groups by forming a carboxylic acid-terminated polyamide and then reacting it with an amino alcohol of 2 to 20 carbon atoms.

[0065] The carboxylic acid-terminated telechelic polyamide segments are prepared by the addition of N-methylaminoethanol or HN(R α )(R β ), where Rα is a C1-C4 alkyl group, and R β is an alcohol group and C2 to C 12 Contains an alkylene group or alternatively R α and R β interconnected to form a ring structure and a C3-C hydroxyl group (as in 2-hydroxymethylpiperidine) 16 Alkylene groups can form, any of which can form polyamides with terminal hydroxyl groups. The reaction of secondary amines (as opposed to hydroxyl groups) with carboxylic acids can be favored by using a 100% molar excess of amino alcohol and conducting the reaction at 160°C + / - 10 or 20°C. The excess amino alcohol can be removed by distillation after the reaction.

[0066] In embodiments using blocked isocyanate groups, the polyisocyanate can be added to the other ingredients (e.g., solvent, polyamide, and any crosslinking compound having three or more Zerewitinoff groups) and packaged for shipment to the end user. When using a conventional unblocked polyisocyanate with polyamide and solvent, the unblocked polyisocyanate is not added until just before the coating, adhesive, or ink is to be used. The unblocked isocyanate groups react rapidly with any Zerewitinoff groups present (depending on temperature and the presence of a urethane-forming catalyst). An optional urethane-forming catalyst may also be blended with either the blocked or unblocked polyisocyanate. These catalysts for urethane formation are well known in the art.

[0067] The polyamide, solvent, and other polymer-forming ingredients (typically present at 50% or greater solids) have a viscosity of less than 10,000 cps, more desirably less than 5,000 cps, and in some embodiments less than 2,000 or 500 cps, and even more desirably about 100-5,000 cps (measured at 50% solids by weight) as measured at 25°C using a Brookfield circular disc viscometer (designations indicating four basic spring torques, such as models LV, RV, HA, and HB) with a circular #6 disc rotating at 5 rpm. The composition may initially be diluted with more solvent if the solids content is greater than 50% in order to measure the viscosity and determine if it is within the required range. These types of viscosities facilitate pouring the polyamide from a 1-gallon paint can or other container into the solvent at 25°C, making the material easier to apply to a substrate.

[0068] The term polyamide oligomer may refer to an oligomer having two or more amide bonds, or the amount of amide bonds may be specified. Generally, polyamide oligomers have at least one diamine component and either at least one diacid component or at least two hydroxycarboxylic acid and / or lactone components (to generate at least two amide bonds). As shown in the examples, polyamides typically have 1 to 20, more preferably 1 to 10, diamines per polyamide oligomer.

[0069] Polyamide oligomers are defined as species having two or more amide bonds per oligomer and a number average molecular weight of less than 5,000 g / mole (e.g., less than 2,500, or 2,000 g / mole). Generally, polyamides have a number average molecular weight of at least 300, more desirably at least 400 g / mole.

[0070] Amide linkages are generally formed from the reaction of a carboxylic acid group with an amine group or from the ring-opening polymerization of lactones (e.g., when an ester bond in a ring structure is converted to an amide bond in a polymer with terminal hydroxyl groups). As previously shown, ring-opening polymerization of lactones can add multiple repeat units from lactones to polyamides. The reaction of a carboxylic acid group with an amine group to form an amide can be catalyzed by boric acid, borate esters, boranes, phosphorous acid, phosphoric acid, phosphate esters, amines, acids, bases, silicic acid, and silsesquioxanes. Additional catalysts, conditions, etc. are available in textbooks such as "Comprehensive Organic Transformations" by Larock.

[0071] The polyamides of the present disclosure may contain small amounts of ester, ether, urethane, urea, and other linkages, provided that the additional monomers used to form these linkages are useful for the intended use of the polymer. This allows other monomers or oligomers to be included in the polyamide to provide specific properties that are desired and not achievable with 100% polyamide segmented oligomers. The addition of polyethers, polyesters, or polycarbonates can result in softer (T g It may be desirable to convert the carboxylic acid end groups or primary or secondary amine end groups of the polyamide to other functional end groups capable of condensation polymerization.

[0072] Preferred amide or tertiary amide forming monomers include dicarboxylic acids, hydroxycarboxylic acids, lactones, diamines, aminocarboxylic acids and lactams.

[0073] Preferred dicarboxylic acids are those in which the alkylene portion of the dicarboxylic acid is a cyclic, straight-chain, or branched alkylene (optionally containing aromatic groups) of 2 to 48 carbon atoms, optionally containing up to one heteroatom per two carbon atoms (or one heteroatom per 10 carbon atoms), more preferably one heteroatom per 8 to 38 carbon atoms (the diacids may contain two more carbon atoms than the alkylene portion or 4 to 50 carbon atoms, more preferably 10 to 40 or 10 to 50 carbon atoms, and in some embodiments 25 to 50 carbon atoms). These include dimer fatty acids, hydrogenated dimer acids, sebacic acid, and the like. In general, applicants prefer diacids with larger alkylene groups, which generally have a lower T g Hydrogenation of dimeric fatty acids reduces their reactivity later on due to the removal of carbon-carbon double bonds by hydrogenation.

[0074] Preferred hydroxycarboxylic acids have 3 to 30 carbon atoms, more preferably 5 to 8. Preferred lactones have 2 to 10 (or 4 to 10) carbon atoms, preferably 5 to 8 carbon atoms.

[0075] Preferred diamines include those having up to 60 carbon atoms, optionally containing one heteroatom (other than the two nitrogen atoms) for every three carbon atoms (or one heteroatom (other than the two nitrogen atoms) for every ten carbon atoms) of the diamine, optionally containing a variety of cyclic, aromatic, or heterocyclic groups in which one or both amine groups are secondary amines, and the preferred formula is: [ka] R b is a direct bond or a straight or branched chain (optionally being or containing a cyclic, heterocyclic, or aromatic moiety) alkylene group of 2 to 36 carbon atoms, more preferably 2 to 12 (or 4 to 12) carbon atoms (optionally containing up to 1 heteroatom per 10 carbon atoms (or 3 heteroatoms per 10) of the diamine); R c and R dare individually straight or branched chain alkylene groups of 1 to 8 carbon atoms, more preferably 1 to 4 (or 2 to 4) carbon atoms, or R c and R d are joined together to form a single straight or branched chain alkylene group of 1 to 8 carbon atoms, or optionally, R c and R d One of the carbon atoms is R b and more preferably R c and R d has 1 to 4 (or 2 to 4) carbon atoms. Such diamines include Albermarle's Ethacure™ 90, N,N'-bis(1,2,2-trimethylpropyl)-1,6-hexanediamine, Huntsman's Clearlink™ 1000 or Jefflink™ 754, N-methylaminoethanol, dihydroxy-, hydroxyl- and amine-, or diamine-terminated poly(alkylene oxide)s in which the alkylene has 2 to 4 carbon atoms and has a molecular weight of 100 to 2000, N,N'-diisopropyl-1,6-hexanediamine, N,N'-di(sec-butyl)phenylenediamine, piperazine, homopiperazine, and methylpiperazine. Jefflink™ 754 has the structure [ka] and Clearlink™ 1000 is a structure [ka] It has the following characteristics.

[0076] In one embodiment, the diamine is HNR 1 -CHR 2 -X-CHR 3 -NR 4 H, where X is a hydrocarbon of 0 to 34 carbon atoms or a direct bond, and R 1 , R 2 , R 3 and R 4is H, an alkyl group as shown below, or an alkylene bridging group as shown below, and the four substituents R 1 , R 2 , R 3 and R 4 At least two of the selected substituents R 1 , R 2 , R 3 and R 4 and is part of an alkylene bridging group between the connection points of the groups, forming a 5- to 7-membered hydrocarbon ring.

[0077] Another diamine having an aromatic group is N,N'-di(sec-butyl)phenylenediamine, see the structure below. [ka]

[0078] In one embodiment, preferred diamines are those in which both amine groups are secondary amines.

[0079] Preferred lactams contain a linear or branched alkylene segment of 4 to 12 carbon atoms, so that the ring structure without the substituent on the lactam nitrogen has a total of 5 to 13 carbon atoms (if including a carbonyl), and the substituent on the lactam nitrogen (if the lactam is a tertiary amide) is an alkyl of 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Dodecyl lactam, alkyl-substituted dodecyl lactam, caprolactam, alkyl-substituted caprolactam, and other lactams with larger alkylene groups have lower T g Lactams are preferred because they provide repeating units having the same value as lactams. Aminocarboxylic acids have the same number of carbon atoms as lactams. Desirably, the number of carbon atoms in the linear or branched alkylene group between the amine and carboxylic acid groups of the aminocarboxylic acid is 4 to 12, and the substituent on the nitrogen of the amine group (if it is a secondary amine group) is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 (or 2 to 4) carbon atoms. Aminocarboxylic acids having secondary amine groups are preferred.

[0080] In one embodiment, desirably 50 wt. % and more desirably at least 60, 70, 80, or 90 wt. % of the polyamide oligomer comprises repeat units from a diacid and a diamine having the following repeat unit structure: [ka] In the formula, R a is the alkylene portion of the dicarboxylic acid, and is a cyclic, straight-chain, or branched (optionally containing aromatic) alkylene of 2 to 48, more preferably 8 to 38, carbon atoms, optionally containing up to one heteroatom per 3 (or 10) carbon atoms in the diacid (the diacid contains 2 more carbon atoms than the alkylene portion of the diacid); R b is a direct bond or a linear or branched (optionally cyclic, heterocyclic, or aromatic moiety(s)) alkylene group of 2 to 36 or 2 to 60 carbon atoms, more preferably 2 to 12 or 4 to 12 carbon atoms (optionally containing up to 1 heteroatom per 10 (or 3 heteroatoms per 10)); R c and R d are each independently a linear or branched alkyl group of 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms (or 2 to 4), or R c and R d are joined together to form a single linear or branched alkylene group of 1 to 8 carbon atoms, or optionally R c and R d One of the carbon atoms is R b and more preferably R c and R d together form an alkylene group of 1 to 4 carbon atoms (or 2 to 4 carbon atoms).

[0081] In one embodiment, desirably 50 wt. % and more desirably at least 60, 70, 80 or 90 wt. % of the polyamide oligomer or telechelic polyamide comprises repeat units from a lactam or aminocarboxylic acid of the structure: [ka] wherein the repeat units may be in various orientations depending on the type of initiator in the oligomer, derived from a lactam or aminocarboxylic acid, and wherein each R e are independently straight or branched alkylene of 4 to 12 carbon atoms, and each R f is independently a straight or branched alkyl of 1 to 8 (more preferably 1 to 4) carbon atoms.

[0082] The polyamides described above are useful for forming solutions with polyisocyanates. Polyisocyanates are used herein to refer to isocyanates, including species with two or more isocyanate groups per molecule. Desirably, the polyamides have end groups that react with isocyanates to form urea and / or urethane linkages. Groups that chemically react with isocyanates to form chemical bonds are known as Zerewitinoff groups and include primary and secondary amines and primary and secondary alcohols. The nitrogen of the primary or secondary amine bonds to the carbonyl of the isocyanate, and a hydrogen from the primary or secondary amine transfers from the amine to the NH group of the isocyanate. The oxygen of the primary or secondary alcohol bonds to the carbonyl of the isocyanate, and a hydrogen from the alcohol's hydroxyl group transfers to the NH group of the isocyanate.

[0083] In a second embodiment, preferred diamines are the specific diamines having the specific structures shown below that provide polyamides soluble at 20-30° C. and that can be the basis for thermosetting liquid compositions that are pourable at 20-30° C. and reasonable solvent content. In a third embodiment, preferred diamines are combinations of diamines having secondary amine end groups in combination with the specific primary diamines below that provide polyamides soluble at 20-30° C. and that can be the basis for thermosetting liquid compositions that are pourable.

[0084] The following are examples of aliphatic, alicyclic, and aromatic diamines with primary amine end groups that, when reacted with aliphatic diacids such as sebacic acid and / or dimer fatty acids, resulted in soluble polyamides. Without wishing to be bound by theory, it is believed that their substantially nonlinear structures, when depicted with appropriate bond angles and lengths and sterically bulky ring structures, result in polyamides that are highly nonlinear, unable to pack closely together, and unable to easily rearrange to strengthen hydrogen bonds to adjacent or nearby amide bonds. Therefore, these and similar polyamines are believed to offer opportunities for solubilization in compatible polar solvents at temperatures between 10 and 150°C. [ka]

[0085] Additionally, two other diamines have been found to tend to form solvent-compatible polyamides useful as components of the present disclosure: 1,5-diamino-2-methylpentane and 4,4'-trimethylenedipiperidine. The structures of these molecules are shown below. [ka]

[0086] The following are examples of aliphatic, cycloaliphatic, and aromatic diamines that, when reacted with aliphatic diacids such as sebacic acid and / or dimer fatty acids, did not result in soluble polyamides. Without wishing to be bound by theory, it is believed that their substantially linear structures, when drawn with the appropriate bond angles and lengths, result in polyamides that are fairly linear and can pack closely together, hydrogen bonding to adjacent or nearby polyamides with minimal opportunity for compatible polar solvents to provide solubilization at temperatures between 10 and 150°C. [ka]

[0087] It is often recognized that the molecular weight of the polyamide portion can also be controlled by using an excess of one component to form end groups for the excess component. For example, an excess of a diamine component (relative to the diacid component) can be used to form an amine-terminated polyamide portion with a controlled or lower molecular weight than would be achieved if a 1:1 stoichiometry between amine and carboxylic acid groups were used. Amine-terminated polyamides react with polyisocyanates to form urea linkages (which generally have a higher softening temperature than the linkages formed between hydroxyl groups and polyisocyanates). Therefore, in some instances, amine-terminated oligomers are reacted with caprolactone to form hydroxyl-terminated polyamides (with a slightly lower softening temperature). Additional caprolactone units can be added to the hydroxyl end groups to form oligomers on the polyamide oligomer from ring-opened caprolactone repeat units. Having polycaprolactone segments helps soften the composition and lowers the softening temperature of the polyamide-rich oligomer.

[0088] The polyamide preparation process has been optimized to produce a waxy, solid telechelic polyamide-rich polymer at room temperature, which can be melted without solvent at temperatures of 100-140°C, more desirably 110-130°C, preferably 120-130°C, to form a liquid telechelic polyamide-rich oligomer that can be blended with compounds that react with the end groups of the telechelic oligomer (Zerewitinoff groups, preferably hydroxyl or amine groups (preferably secondary amine groups) to form covalent bonds). Then, while the telechelic oligomer is liquid at elevated temperature (and before, during, or after the addition of the compound that reacts with the telechelic end groups), a solvent is added to convert the polyamide-rich composition to an easily stirrable liquid (viscosity at 50 wt% solids using a Brookfield spinning disk / spindle viscometer of less than 10,000 or 5,000 cps, in some embodiments less than 2,000 or 500 cps, more desirably about 100-5,000 cps, at 25°C using a rotation speed of 5 rpm and a #6 spindle).

[0089] Useful solvents for the present disclosure have a boiling point at 1 atmosphere of 40-120°C and contain 2-10 carbon atoms, one or more oxygen atoms, and one or more hydrogen atoms. Examples of compounds used as solvents include isopropanol, acetone, dimethyl carbonate, and butyl acetate.

[0090] Suitable polyisocyanates have an average of at least about two isocyanate groups per molecule, preferably an average of from about two to about four isocyanate groups, and include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates, as well as their oligomerization products, used alone or in mixtures of two or more. Diisocyanates are more preferred.

[0091] Specific examples of suitable aliphatic polyisocyanates include α,ω-alkylene diisocyanates having 5 to 20 carbon atoms, such as hexamethylene-1,6-diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, and 2-methyl-1,5-pentamethylene diisocyanate. Polyisocyanates having fewer than 5 carbon atoms can be used, but are less preferred due to their high volatility and toxicity. Preferred aliphatic polyisocyanates include hexamethylene-1,6-diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.

[0092] Specific examples of suitable cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate (commercially available as Desmodur™ W from Bayer Corporation), isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis-(isocyanatomethyl)cyclohexane, etc. Preferred cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

[0093] Specific examples of suitable araliphatic polyisocyanates include m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, etc. A preferred araliphatic polyisocyanate is tetramethylxylylene diisocyanate.

[0094] Examples of suitable aromatic polyisocyanates include 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate, isomers thereof, naphthalene diisocyanate, etc. Preferred aromatic polyisocyanates include 4,4'-diphenylmethylene diisocyanate and toluene diisocyanate.

[0095] Examples of suitable heterocyclic isocyanates include 5,5'-methylenebisfurfuryl isocyanate and 5,5'-isopropylidenebisfurfuryl isocyanate.

[0096] In some embodiments of the present invention, blocked isocyanate reactants may be used to minimize reaction of the isocyanate groups and increase the intrinsic viscosity until the correct time to allow for the molecular weight of the reactants to increase. Blocked isocyanate groups are well known in the art, and compounds with blocked isocyanate groups are commercially available, with at least one blocked isocyanate compound being shown in the examples. Typically, blocked isocyanate groups are thermally deblocked by heating the reactants. Several blocked isocyanate compounds have been described in the literature, using well-known ketoxime chemistry.

[0097] In some embodiments, low molecular weight polyols and / or polyamines are used to provide "chain extension" and / or "crosslinking" of reaction mixtures containing isocyanate-terminated reactants or polyisocyanates. Examples include low molecular weight polyols and polyamines having a number average molecular weight of less than about 500 daltons. "Polyol" in this context refers to any product having an average of about two or more hydroxyl groups per molecule. Polyamines in this context are used to describe compounds having two or more primary or secondary amine groups that can react with isocyanate groups to form urea linkages. Specific examples include aliphatic, cycloaliphatic, and aromatic polyols, particularly diols having 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms, such as 1,4-butanediol. Specific examples of polyamines include aliphatic, cycloaliphatic, and aromatic polyamines, particularly diamines and triamines having 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms, such as ethylenediamine and similar alkylenediamines and triamines. Polyamines can include hydrazine and compounds formed by reacting hydrazine with diacids, such as adipic acid dihydrazide.Low molecular weight compounds are preferred because they move faster in the composition than oligomeric or polymeric species.Any other compounds known to function as chain extenders for polyester polyols and polyamides can also be used.

[0098] In some embodiments, trifunctional isocyanate compounds and higher isocyanate-functional polyisocyanates can be used. These may be formed by trimerizing low-functionality diisocyanates or by reacting di- and / or triisocyanates with triols, tetrahydric alcohols, and higher-functional alcohols. They may also be made by reacting triamines and higher-functional amines with diisocyanates and / or triisocyanates. Other polyfunctional isocyanate compounds may be made from trifunctional or higher amines and conventional reactions that convert the amine groups to isocyanate groups.

[0099] Preferred epoxy resins are liquid resins based on bisphenol compounds, particularly bisphenol A, bisphenol F, or bisphenol A / F, available from Dow, Huntsman, Hexion, etc. These liquid resins have low viscosity compared to epoxy resins and, in their fully cured state, have excellent coating properties. They may optionally be present in combination with solid bisphenol A resins or bisphenol F novolac epoxy resins.

[0100] Also suitable as epoxy resins are aliphatic or cycloaliphatic polyepoxides, such as saturated or unsaturated, branched or unbranched, cyclic or open-chain C2-C6 30 Glycidyl ethers of diols, such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol or dibromo-neopentyl glycol, glycidyl ethers of tri- or tetrafunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyols, such as castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, and alkoxylated glycerol or alkoxylated trimethylolpropane; hydrogenated bisphenol A, F or A / F liquid resins, or glycidylation products of hydrogenated bisphenol A, F or A / F; N-glycidyl derivatives of amide or heterocyclic nitrogen bases, such as triglycidyl cyanurate and triglycidyl isocyanurate, and reaction products from epichlorohydrin and hydantoin.

[0101] Finally, other suitable epoxy resins are those from the oxidation of olefins, for example vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0102] The epoxy resin may contain a reactive diluent, in particular a reactive diluent having at least one epoxide group. Suitable reactive diluents are, for example, glycidyl ethers of mono- or polyhydric phenols and aliphatic or cycloaliphatic alcohols.

[0103] Other additives well known to those skilled in the art can be used to aid in the preparation of the thermosetting compositions of the present invention. Such additives include surfactants, stabilizers, defoamers, flash rust inhibitors, adhesion promoters, lubricants, surface tension modifiers, plasticizers, thickeners, leveling agents, antimicrobial agents, fungicides, antioxidants, UV absorbers, slip modifiers, flame retardants, pigments, fillers, dyes, and the like. These additives are well known in the art and can be added at any stage of the manufacturing process. All of these are used in conventional amounts for conventional purposes in coatings and adhesives.

[0104] As coating compositions or adhesives, the compositions of the present disclosure can be applied to any substrate, including wood, metal, glass, fabric, leather, paper, plastic, foam, etc., by any conventional method, including brushing, dipping, flow coating, spraying, etc. They protect the substrate from a variety of environmental agents, such as water, chemicals, corrosives, dirt, ozone, soot, etc., and provide an easily cleaned surface.

[0105] The compositions of the present invention and their formulations are useful as self-supporting films, coatings on various substrates, or adhesives having longer service lives or other improved properties than similar polyurethane compositions.

[0106] example: Definition of Reactant H-dimer fatty acid - (usually a hydrogenated dimer formed from conventional fatty acids (molecular weight approximately 565 g / mol molecular weight) Piperazine - piperazine (molecular weight approximately 86 g / mol) Caprolactone-caprolactone (approximately 114 g / mol) Sebacic acid-1,8-octanedicarboxylic acid (approximately 202 g / mol) MPDA—4,4′-methylenebis(2-methylcyclohexylamine), (molecular weight approximately 238.4 g / mol) mPDA-metaphenylenediamine (molecular weight approximately 86 g / mol) Verstanat™ B 1186A - 60 wt. % blocked isocyanate in naphtha, 7.1 NCO content, aliphatic, from Evonik; the blocking agent may be ε-caprolactam. Desmodur™ 5375—4,4′-methylenedicyclohexyl diisocyanate (molecular weight approximately 262.35 g / mol) available from Covestro. Desmodur™ N3600—Hexamethyldiisocyanate (HDI) trimer available from Covestro. Trimethylolpropane-Trimethylolpropane DBE - a mixture of dimethyl adipate, dimethyl glutarate, and dimethyl succinate available from Sigma Aldrich; CH3O2C(CH2) n CO2CH3 (n=2, 3, 4). DMC - Dimethyl Carbonate Xylene-Xylene Acetone-Acetone Butyl Acetate - Butyl Acetate Polyamide Synthesis

[0107] The diamine and diacid monomers are added to the reactor. The reactor is flushed with nitrogen and kept under an inert atmosphere. The reactor is heated to 160°C and held at that temperature for 2 hours, then further heated to 200°C and held at that temperature for 48 hours or until the acid number in the reactor is below 1 (mg KOH / g). Water is formed during the reaction and can be distilled from the reactor. The reactor is then 180℃ Cool ,the The other monomers are added. The reactor temperature is maintained at 180°C for 10 hours. The final polyamide is a waxy solid at room temperature with a melting point close to or above 100°C. [Table 1]

[0108] (1-Component, Baking with Blocked Isocyanate Polyamide Coating) Instructions: The polyamide polyol was melted at 130°C, and high-boiling solvents (DBE and butyl acetate) were added to the melt to dilute the polyol. The solution was then cooled to 60°C, and the other ingredients were added. The solution was then further cooled to room temperature. The resulting solvent-based coating solution is a low-viscosity liquid. The coating is produced by first casting a film onto a substrate, then drying the film at a moderate temperature (80°C) for 10 minutes, and then baking at 150°C for 30 minutes. [Table 2] [Table 3] [Table 3a]

[0109] Procedure for two-component (polyamide polyol and polyisocyanate) solvent-based coatings: The polyamide polyol was melted at 130°C, and high-boiling solvents (DBE and butyl acetate) were added to the melt to dilute the polyol. The solution was then cooled to 60°C, and the extender and DBTL catalyst were also added to the solution. The solution was then further cooled to room temperature. The resulting solvent-based polyol solution is a low-viscosity liquid. Coatings are produced by first mixing the polyol solution components with the isocyanate component at room temperature, and then a film is cast onto the substrate. The film was allowed to dry at room temperature for 7 days before testing. [Table 4] [Table 5] [Table 5a]

[0110] In the following examples, hydroxyl (OH) number was determined using the TSI method (ASTM E1899), acid number was determined by titration using NaOH titrant and methylene blue indicator, and viscosity was measured using a Brookfield DV-E viscometer using an LV spindle at either 60 rpm or 30 rpm depending on the viscosity of the material, as would be understood by one familiar with the use of viscometers.

[0111] Example 1 (Polyamide Synthesis): 750 parts of hydrogenated dimer acid were mixed with 221 parts of metaphenylenediamine in a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and evaporated from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. 166 parts of epsilon-caprolactone were then added to the reactor and reacted at 180°C for 12 hours. The resulting polyamide was a dark yellow product with an OH value of 74.5 and a melt viscosity of 25,000 cP at 100°C.

[0112] Example 2 (Polyamide Synthesis): 750 parts of hydrogenated dimer acid were mixed with 164 parts of piperazine in a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and evaporated from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. 134 parts of epsilon-caprolactone were then added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a pale yellow product with an OH value of 65.9 and a melt viscosity of 3,100 cP at 100°C.

[0113] Example 3 (Polyamide Synthesis): 299 parts sebacic acid and 291.7 parts dodecadioic acid were mixed with 465.4 parts 250 g / mol polytetramethylene oxide and 42.2 parts piperazine in a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and evaporated from the reactor. After 48 hours, the acid number of the mixture was less than 1 mg KOH / g. The resulting polymer was a pale yellow product with an OH number of 65.8 and a melt viscosity of 650 cP at 100°C.

[0114] Example 4 (Polyamide Synthesis): 620.5 parts of hydrogenated dimer acid were mixed with 285.5 parts of isophorone diamine in a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and evaporated from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. 134 parts of epsilon-caprolactone were then added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a pale yellow product with an OH value of 65.9 and a melt viscosity of 19,000 cP at 100°C.

[0115] Example 5 (Polyamide Synthesis): 509.2 parts of hydrogenated dimer acid were mixed with 371.9 parts of 4,4'-methylenebis(2-methylcyclohexylamine) under a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and evaporated from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. 152.1 parts of epsilon-caprolactone were then added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a pale yellow product with an OH value of 74.5 and a melt viscosity of 15,000 cP at 100°C.

[0116] Example 6: 128g of propylene glycol monomethyl ether acetate was combined with 10.5g of Lubrizol Solsperse® M387 polymeric dispersant and 30g of BASF Laropal® A81 aldehyde resin and mixed at 500 RPM until uniform. 392g of rutile titanium dioxide was added and mixed at 1500 RPM using a Cowles blade until a 7+ Hegman grind was obtained using a Hegman gauge. 127.4 g of the polyamide of Example 1 was added along with 34.3 g of dipropylene glycol dimethyl ether, 34.3 g of dimethyl carbonate, 140 g of methyl ethyl ketone, and 0.45 g of dibutyltin dilaurate, then mixed at 500 RPM for 15 minutes, and 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed at 500 RPM for 10 minutes.

[0117] Example 7: 73 g of propylene glycol monomethyl ether acetate was combined with 6 g of Lubrizol Solsperse® M387 polymeric dispersant, 17 g of BASF Laropal® A81 aldehyde resin, and 2.5 g of BYK-052 N silicone-free defoamer, then mixed at 500 RPM until homogeneous. 224 g of rutile titanium dioxide was added and mixed at 1500 RPM using a Cowles blade until a Hegman grind of 7+ was obtained. 320 g of the polyamide from Example 2 was added along with 96 g of methyl ethyl ketone, 96 g of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and 1.6 g of dibutyltin dilaurate, then mixed at 500 RPM for 15 minutes. 192 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0118] Example 8: 128 g of propylene glycol monomethyl ether acetate was combined with 10.5 g of Lubrizol Solsperse® M387 polymeric dispersant and 30 g of BASF Laropal® A81 aldehyde resin, then mixed at 500 RPM until uniform. 392 g of rutile titanium dioxide was added and mixed at 1500 RPM using a Cowles blade until a grind of 7+ Hegman was obtained using a Hegman gauge. 196 g of the polyamide from Example 3 was added along with 140 g of methyl ethyl ketone and 0.45 g of dibutyltin dilaurate, then mixed at 500 RPM for 15 minutes. 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0119] Example 9: 128g of propylene glycol monomethyl ether acetate was combined with 10.5g of Lubrizol Solsperse® M387 polymeric dispersant and 30g of BASF Laropal® A81 aldehyde resin, then mixed at 500 RPM until uniform. 392g of rutile titanium dioxide was added and mixed at 1500 RPM using a Cowles blade until a 7+ Hegman grind was obtained. 196g of Asahi Masei Duranol® T5652 polycarbonate polyol was added along with 140g of methyl ethyl ketone and 0.45g of dibutyltin dilaurate, then mixed at 500 RPM for 15 minutes. 98g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0120] Example 10: 128g of propylene glycol monomethyl ether acetate was combined with 10.5g of Lubrizol Solsperse® M387 polymeric dispersant and 30g of BASF Laropal® A81 aldehyde resin, then mixed at 500 RPM until uniform. 392g of rutile titanium dioxide was added and mixed at 1500 RPM using a Cowles blade until a grind of 7+ Hegman was obtained using a Hegman gauge. 196g of Panolam Piothane® 67-2000 HNA polyester polyol was added along with 140g of methyl ethyl ketone and 0.45g of dibutyltin dilaurate, then mixed at 500 RPM for 15 minutes. 98g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0121] The compositions of Examples 6 through 10 were coated onto cold-rolled steel according to ASTM D523-08. For the examples set forth in Table 6 below, initial viscosity ("IV") was determined using ASTM D4287-10, spindle #3, 100 RPM, average 60° gloss ("Gloss") was determined using ASTM D523-08, average 60° haze ("Haze"), average 60° clarity of image ("DOI") was determined using ASTM D4039-09, average 7-day Konig hardness ("Hardness") was determined using ASTM D4366, flexibility ("Flex") was determined using ASTM D522-13, impact (direct / reverse) ("Impact") was determined using ASTM D2794-93, and average 1-day wet crosshatch adhesion ("Adhesion") was determined using ASTM D3359-17. [Table 6]

[0122] Except in the examples or where otherwise indicated, all numerical quantities herein specifying amounts, reaction conditions, molecular weights, numbers of carbon atoms, etc., are understood to be modified by the word "about." Unless otherwise indicated, all percentages and formulation values ​​are on a molar basis.

[0123] Unless otherwise indicated, all molecular weights are number average molecular weights. Unless otherwise indicated, each chemical or composition referred to herein should be understood to be a commercial grade material that may include isomers, by-products, derivatives, and other such materials commonly understood to be present in commercial grades.

[0124] As used herein, "consisting essentially of" permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration. All embodiments of the invention described herein are contemplated and may be read from both an open-ended and inclusive perspective (i.e., using the language "comprising") and a closed and exclusive perspective (i.e., using the language "consisting of").

[0125] As used herein, parentheses are used to 1) indicate that something is optionally present, such as when monomer(s) means one or more monomers, or when (meth)acrylate means methacrylate or acrylate; 2) modify or further define the preceding term; or 3) list narrower embodiments.

[0126] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the subject invention. The present invention provides, for example, the following items. (Item 1) 1. A thermosetting composition comprising: a) 10 to 75 wt. % of a polyamide oligomer having predominantly at least two amide bonds and two end groups selected from amine end groups, hydroxyl end groups, or carboxylic acid end groups; b) 10 to 50 wt. % of a diisocyanate or polyisocyanate component (optionally where the isocyanate reactivity is temporarily blocked) that reacts with amine, carboxyl, and / or hydroxyl groups to form covalent chemical bonds; c) optionally one or more non-reactive organic diluents; d) up to 50% by weight of one or more compounds having a molecular weight of less than 500 g / mole and having three or more groups reactive with isocyanates selected from the group of amine groups and hydroxyl groups, the thermosetting compositions of a), b), c), and d) prior to reaction of the end groups selected from amine end groups, hydroxyl end groups, or carboxylic acid end groups with the isocyanate groups have an average functionality of all isocyanate end groups, amine end groups, hydroxyl end groups, and carboxylic acid end groups of 2.1 or more per molecule; the weight percentages are based on the total components of the thermosetting composition; A thermosetting composition, wherein the composition, prior to reaction of the diisocyanate or polyisocyanate, when at 50% solids or diluted to 50%, has a viscosity of less than 10,000 cps at 25°C as measured on a Brookfield rotating disc viscometer using a rotation speed of 5 rpm and a #6 spindle. (Item 2) The polyamide oligomer is a) a diamine having two amine groups capable of forming a covalent bond with the carbonyl of a carboxylic acid, selected from the group consisting of diamines having 4 to 60 carbon atoms with two secondary terminal amine groups and / or diamines having 4 to 60 carbon atoms with one or two primary amine groups, b) polyamide repeat units derived from polymerizing lactone and / or carboxylic acid monomers, The lactone or carboxylic acid unit is C 5 ~C 8 Lactone, C 5 ~C 8 Item 1, the thermosetting composition according to item 1, derived from an acid component selected from the group consisting of a hydroxycarboxylic acid and an aliphatic dicarboxylic acid of 4 to 50 carbon atoms, the lactone and / or carboxylic acid monomer forming repeating units, and the carbonyl from the lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid reacting with a primary or secondary amine nitrogen to form an amide bond, thereby forming a polyamide oligomer. (Item 3) 3. The thermosetting composition according to item 2, wherein at least 40 mole percent of the diamines are cyclic diamines having 4 to 15 carbon atoms, wherein the nitrogen atoms are in secondary amine groups and part of one or more rings. (Item 4) Item 4. The thermosetting composition according to item 2 or 3, wherein at least 50 mol% of the diamine is a diamine having two primary amine groups, and the diamine having two primary amine groups has the following structure: [ka] (Item 5) 5. The thermosetting composition of any one of items 2 to 4, wherein the polyamide oligomer is composed of repeat units from a dicarboxylic acid reacted with an amine group, and at least 50 mole % of the dicarboxylic acid components within the amide repeat units are dicarboxylic acids of 10 to 50 carbon atoms. (Item 6) 6. The thermosetting composition according to any one of items 2 to 5, wherein at least 50 wt.% of the repeat units from carboxylic acid are derived from dimer fatty acid. (Item 7) 7. The thermosetting composition according to any one of items 2 to 6, wherein the combined repeat units of a diamine and a lactone and / or a carboxylic acid monomer that form at least one amide bond during their polymerization into the polyamide are 20 to 60 wt % of the thermosetting composition. (Item 8) 8. The thermosetting composition according to any one of items 2 to 7, wherein the combined repeat units of diamine and lactone and / or carboxylic acid monomer that form at least one amide bond during their polymerization into the polyamide are 25 to 50 wt % of the thermosetting composition. (Item 9) 9. The thermosetting composition according to any one of items 2 to 8, wherein at least 90% by weight of the repeat units from diamines are derived from cyclic and / or bicyclic diamines of 4 to 15 carbon atoms, and the nitrogen atoms of the diamines are part of a cyclic structure. (Item 10) 10. The thermosetting composition of any one of the preceding claims, wherein the reactive polyisocyanate or blocked isocyanate, when both are present, in combination, is present in solution in an amount of about 10 to 50% by weight of the solution, based on the weight of all components in the composition. (Item 11) 11. The thermosetting composition of any one of items 1 to 10, wherein the organic diluent is present at about 10 to about 50% by weight of the composition. (Item 12) Item 12. The thermosetting composition according to item 11, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate. (Item 13) 13. The thermosetting composition according to any one of the preceding items, wherein the solution after evaporation of the solvent is thermosetting. (Item 14) 14. The thermosetting composition according to any one of items 1 to 13, wherein the polyisocyanate component has two or more isocyanate groups per polyisocyanate, and the ratio of isocyanate groups to combined hydroxyl groups, amino groups, and / or carboxyl groups of the polyisocyanate is 2:1 to 1:1. (Item 15) 15. The thermosetting composition of any one of the preceding claims, wherein as the organic diluent evaporates, the polyamide oligomer is crosslinked via reaction with the polyisocyanate component reacting with hydroxyl, carboxyl, and / or amino groups to form covalent chemical bonds to produce a polymer of number average molecular weight of at least 1,000,000 g / mol. (Item 16) 16. The thermosetting composition of any one of the preceding items formed into a free-standing film, coating, or adhesive. (Item 17) 1. A method for forming a thermosetting coating or film, comprising: a) polymerizing a diamine selected from the group consisting of a diamine having 4 to 60 carbon atoms and having two secondary terminal amine groups and a diamine having two primary amine groups, wherein the diamine having two primary amine groups optionally has the structure:

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Claims

1. 1. A thermosetting composition comprising: a) 10 to 75 weight percent of a polyamide oligomer having predominantly at least two amide linkages and two end groups selected from amine, hydroxyl, or carboxylic acid end groups, said polyamide oligomer being polyamide repeat units derived from polymerizing with a cyclic, heterocyclic, or aromatic diamine; b) 10 to 50 weight percent of a diisocyanate or polyisocyanate component (optionally where the isocyanate reactivity is temporarily blocked) that reacts with amine, carboxyl, and / or hydroxyl groups to form covalent chemical bonds; c) one or more non-reactive organic diluents; d) up to 50% by weight of one or more compounds having three or more groups reactive with isocyanates selected from the group of amine groups and hydroxyl groups and having a molecular weight of less than 500 g / mole; the thermosetting compositions of a), b), c), and d) prior to reaction of the end groups selected from amine end groups, hydroxyl end groups, or carboxylic acid end groups with the isocyanate groups have an average functionality of all isocyanate end groups, amine end groups, hydroxyl end groups, and carboxylic acid end groups of 2.1 or greater per molecule; the weight percentages are based on the total components of the thermosetting composition; A thermosetting composition, wherein the composition, prior to reaction of the diisocyanate or polyisocyanate, when at 50% solids or diluted to 50%, has a viscosity of less than 10,000 cps at 25°C as measured by a Brookfield rotating disk viscometer using a rotation speed of 5 rpm and a #6 spindle.

2. The polyamide oligomer is a) a diamine having two amine groups capable of forming a covalent bond with the carbonyl of a carboxylic acid, selected from the group consisting of diamines having 4 to 60 carbon atoms with two secondary terminal amine groups and / or diamines having 4 to 60 carbon atoms with one or two primary amine groups, b) polyamide repeat units derived from polymerizing lactone and / or carboxylic acid monomers, The lactone or carboxylic acid unit is C ５ ~C ８ Lactone, C ５ ~C ８ 10. The thermosetting composition of claim 1, wherein the polyamide oligomer is derived from an acid component selected from the group consisting of a hydroxycarboxylic acid and an aliphatic dicarboxylic acid of 4 to 50 carbon atoms, and the lactone and / or carboxylic acid monomers form repeat units in which carbonyls from the lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid react with primary or secondary amine nitrogens to form amide bonds, thereby forming a polyamide oligomer.

3. 3. The thermosetting composition of claim 2, wherein at least 40 mole percent of the diamines are cyclic diamines in which the nitrogen atoms are secondary amine groups and part of one or more rings and have 4 to 15 carbon atoms.

4. 4. The thermosetting composition of claim 2 or claim 3, wherein at least 50 mole percent of the diamine is a diamine having two primary amine groups, and the diamine having two primary amine groups has the following structure: 【Chemistry 19】

5. 5. The thermosetting composition of claim 2, wherein the polyamide oligomer is comprised of repeat units from a dicarboxylic acid reacted with an amine group, and wherein at least 50 mole percent of the dicarboxylic acid components present in the amide repeat units are dicarboxylic acids of 10 to 50 carbon atoms.

6. 6. The thermosetting composition of claim 2, wherein at least 50% by weight of the repeat units from carboxylic acids are derived from dimer fatty acids.

7. 7. The thermosetting composition of claim 2, wherein the combined repeat units of diamine and lactone and / or carboxylic acid monomers that form at least one amide bond during their polymerization into the polyamide are 20 to 60 wt. % of the thermosetting composition.

8. 8. The thermosetting composition of claim 2, wherein the combined repeat units of diamine and lactone and / or carboxylic acid monomers that form at least one amide bond during their polymerization into the polyamide are 25 to 50 wt. % of the thermosetting composition.

9. 9. The thermosetting composition of claim 2, wherein at least 90% by weight of the repeat units from the diamine are derived from cyclic and / or bicyclic diamines of 4 to 15 carbon atoms, and wherein a nitrogen atom of the diamine is part of a cyclic structure.

10. 10. The thermosetting composition of any one of claims 1 to 9, wherein the reactive polyisocyanate or blocked isocyanate, when both are present, in combination, is present in solution in an amount of about 10 to 50 weight percent of the solution, based on the weight of all components in the composition.

11. 11. The thermosetting composition of any one of claims 1 to 10, wherein the organic diluent is present at about 10 to about 50 weight percent of the composition.

12. 12. The thermosetting composition of claim 11, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate.

13. 13. The thermosetting composition of claim 1, wherein the solution after evaporation of the solvent is thermosetting.

14. 14. The thermosetting composition of any one of claims 1 to 13, wherein the polyisocyanate component has two or more isocyanate groups per polyisocyanate, and the ratio of isocyanate groups to combined hydroxyl groups, amino groups, and / or carboxyl groups of the polyisocyanate is from 2:1 to 1:

1.

15. 15. The thermosetting composition of any one of claims 1 to 14, wherein as the organic diluent evaporates, the polyamide oligomer is crosslinked via reaction with the polyisocyanate component reacting with hydroxyl, carboxyl, and / or amino groups to form covalent chemical bonds to produce a polymer of number average molecular weight of at least 1,000,000 g / mole.

16. 16. The thermosetting composition of any one of claims 1 to 15 formed into a free-standing film, coating, or adhesive.

17. 1. A method for forming a thermosetting coating or film, comprising: a) polymerizing a diamine selected from the group consisting of a diamine having 4 to 60 carbon atoms and having two secondary terminal amine groups and a diamine having two primary amine groups, wherein the diamine is derived from a cyclic, heterocyclic, or aromatic diamine, and the diamine having two primary amine groups optionally has the following structure: 【Chemistry 20】 reacts with a carboxylic acid group, and the carboxylic acid unit is C ５ ~C ８ Lactone, C ５ ~C ８ from lactone and / or carboxylic acid components selected from the group consisting of hydroxycarboxylic acids and aliphatic dicarboxylic acids of 4 to 50 carbon atoms, forming repeat units with a carbonyl or nitrogen as part of an amide bond, thereby forming a polyamide oligomer, said polyamide oligomer having at least two end groups selected from amine groups, carboxyl groups, or hydroxyl groups; b) optionally heating the polyamide oligomer to a temperature of 100-150°C to make it a more processable liquid; c) adding one or more non-reactive organic diluents; d) adding to the polyamide oligomer, optionally, 10 to 40 weight percent of a polyisocyanate component having blocked isocyanate groups that react with hydroxyl, carboxyl, and / or amino groups to form covalent chemical bonds with the nitrogen of the amino group or the oxygen of the hydroxyl group or reaction of the carboxyl group with an isocyanate group, hydroxyl group, or amine group; the weight percent of diamine and carboxylic acid repeat units in the solution is 10 to 75 weight percent, the amount of organic diluent is up to 50 weight percent of the solution, the amount of the components reactive with hydroxyl, carboxyl, and / or amino groups is 10 to 40 weight percent of the solution, and at 50% solids, the solution prior to reacting with the polyisocyanate has a viscosity of less than 10,000 cps at 25°C as measured by a Brookfield spinning disk viscometer at 5 rpm and using a #6 spindle.

18. 18. The method of claim 17, wherein the organic diluent is evaporated from the solution and the isocyanate groups react with hydroxyl, carboxyl, and / or amino groups to form covalent bonds.

19. 19. The method of claim 18, wherein at least 50 mole percent of the diamines are cyclic diamines in which the nitrogen atoms are secondary and part of a ring and have from 4 to 15 carbon atoms.

20. 19. The method of claim 18, wherein at least 50 mole percent of the diamine is a diamine having two primary amine groups, and the diamine having two primary amine groups has the following structure: 【Chemistry 21】

21. 21. The method of any one of claims 17 to 20, wherein at least 50% by weight of the repeat units from carboxylic acids are derived from dicarboxylic acids of 10 to 50 carbon atoms.

22. 22. The method of claim 21, wherein at least 50% by weight of the repeat units from carboxylic acids are derived from dimer fatty acids.

23. 21. The method of any one of claims 17 to 20, wherein the component that reacts with hydroxyl groups, carboxyl groups, and / or amino groups is a blocked polyisocyanate having two or more isocyanate groups in a chemically blocked form that can be deblocked by thermal heating, and the blocked polyisocyanate can be added to the polyamide oligomer without chemical reaction until the blocked isocyanate groups are unblocked.

24. 24. The method of any one of claims 17 to 23, further comprising a process step in which up to 25% by weight of one or more compounds having a molecular weight of less than 500 g / mol and having three or more groups reactive with isocyanates selected from the group of amine groups, carboxyl groups, and hydroxyl groups are added to the composition to promote crosslinking of the final composition.

25. 18. The method of claim 17, wherein the polyisocyanate is not added until the composition is ready to form a coating or film, and upon addition of the polyisocyanate to the polyamide oligomer, the polyisocyanate begins to react with the polyamide oligomer through its isocyanate groups.

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