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

Abstract

The present invention relates to a thermosetting polymer solution, such as a polyurethane and / or polyurea, comprising a polyamide sufficient to provide polyamide strength, adhesion, and durability, wherein the polymer solution may be prepared as a one-component or two-component solvent-based coating composition. The polyamide is harder, has higher chemical resistance, and often provides stronger thermosetting properties than similar water-based polyurethanes rich in polyamide. The compositions of the present disclosure differ from other polyamides in that they are formulated to a viscosity suitable for use as a coating and subsequently have a crosslinking technique to form a rigid thermosetting film.

Description

Technology Field

[0001] The present invention relates to a polymer system based on a hydroxyl, amine, or carboxylic acid-terminated polyamide-rich oligomer reacted with a polyisocyanate (optionally blocked) or a polyepoxide to produce a thermosetting solvent-borne ink and coating composition. These may be a one-component system or a two-component system. Background Technology

[0002] Due to hydrogen bonding associated with amide linkages, polyamides are generally processed during the melting stage, or, in the case of some very rigid aromatic polyamide chains, through a process in which the chains are oriented during processing. Polyamides can have very high strength and good barrier properties.

[0003] International Publications WO 2014 / 126739 A1 and WO 2014 / 126741 A2 were filed by the same applicant and disclose the use of such telechelic polyamides in telechelic N-alkylated polyamide polymers and water-borne polyamide-urea dispersions.

[0004] One objective was to manufacture a new, improved polyamide-rich crosslinkable (thermosetting) polymer system that can be used in coating compositions having a higher level of performance than the earlier International Publication WO 2014 / 126741 A2 based on aqueous polyamides. Aqueous systems inherently have a problem with the surface-active moiety included to facilitate the formation of an aqueous dispersion. Surface-active species tend to bind to the final coating at the interface where individual particles of the polyamide dispersion attempt to fuse together into an agglomerate barrier film. To some extent, the surface-active rich phase in the final coating can reduce the strength of the final film and allow water and other polar species to penetrate more easily through the final film. Annealing the coating from the aqueous dispersion can improve the fusion of individual particles and facilitate the migration of surface-active species from the interface between particles.

[0005] If solvent-based polyamide-rich compositions can be developed with small amounts of solvent and / or solvents acceptable to the coating industry, such compositions are expected to possess improved mechanical and barrier properties compared to water-based polymer dispersions. However, there are several inherent challenges in manufacturing solvent-based polyamide-rich compositions for coatings or inks. First, many common solvents are unsuitable for polyamides. Due to hydrogen bonding, polyamides tend to remain solid at room temperature and up to approximately 130°C. While solvents suitable for coatings generally evaporate rapidly at temperatures of 15°C or slightly higher, thus eliminating the need for heating to transition the coating from a wet film to a dry film when using these solvents, it is difficult to incorporate these solvents into the polyamide at temperatures above 100°C. Furthermore, the compatibility of polyamides with solvents decreases as their molecular weight increases.

[0006] Another objective is to produce cross-linked polyamide-rich coatings for various substrates from a liquid polymer composition at room temperature (e.g., 20 to 25°C, preferably 24°C) with minimal use or release of hazardous organic solvents (intending to use the minimum amount of organic solvent and such solvent that is most acceptable and has the lowest risk level for the coating industry).

[0007] It has been found that dicarboxylic acids are preferred for forming polyamides having 4 to 50 (optional 10 to 50) carbon atoms, and that these provide polyamides that are easier to process. Examples of dicarboxylic acids include sebacic acids and dimeric fatty acids. The inventors have found that it is desirable to have a diamine having a second amine terminal group and / or a bent structure so as to often prevent effective or strong hydrogen bonding of the amide linkage or diamine in the polyamide, with a sterically bulky substituent on a carbon atom adjacent to a primary nitrogen group, such that the two nitrogen atoms forming the amide linkage of the polyamide (derived from the diamine component) are rigidly positioned relative to each other and can prevent the nitrogen or amide linkage from forming strong hydrogen bonds with other amide links on the polyamide. Such diamines that interfere with hydrogen bonding near the amide linkage make the resulting polyamide easier to process as a melt and solvent-based composition. These diamines may be selected from cyclic diamines, such as piperazine, 4,4'-trimethylenepiperidine, specific diamines of phenylene, specific diamines of diphenylmethylene, etc. It was not anticipated that flexibility between the carboxylic acid moiety and the double hydrocarbon chain or ring, and single hydrocarbon chains, are more desirable in the diamine component to achieve a polyamide that is easy to process at 25°C or only slightly higher.

[0008] The inventors have developed a method to increase the molecular weight of a polyamide-rich polymer in a composition to crosslink the composition to make it thermosetting. The inventors have also developed a method to incorporate other softer polymer segments and softer polymer segments into the composition to facilitate making the composition swollen into a liquid coating composition having a viscosity suitable for applying otherwise hard and waxy polyamide solvents as a coating.

[0009] The issue of solvent volatility is partially resolved by using solvent blends that allow heating to a temperature at which the polyamide and solvent can be blended if necessary. Solvent volatility is partially controlled by using a highly polymer-rich composition. The solvent-swelling polyamide-rich composition is formulated into a high-polymer solid to minimize solvent recovery and solvent release into the environment during film formation.

[0010] The following embodiments of the subject matter are considered:

[0011] 1. As a thermosetting composition,

[0012] a) 10 to 75 weight% of a polyamide oligomer having two terminal groups selected from amine, hydroxyl, or carboxylic acid terminal groups and at least two amide links,

[0013] b) 10 to about 40 or 50 weight percent of a di or polyisocyanate component that reacts with amine, carboxyl, and / or hydroxyl groups to form a covalent chemical bond (where isocyanate reactivity is optionally temporarily blocked),

[0014] c) optionally one or more non-reactive organic diluents, and

[0015] d) a compound with a molecular weight of less than 500 g / mole (not a polyamide) having three or more groups reactive with an isocyanate selected from the group of amines and hydroxyl groups, at most 50, more preferably only 40 or 25 wt%; comprising,

[0016] The thermosetting compositions of a), b), c), and d) prior to the reaction between the terminal group selected from amine, hydroxyl, or carboxylic acid terminal groups and the isocyanate group have an average functionality of at least 2.1 per molecule of all isocyanate, amine, hydroxyl, and carboxylic acid terminal groups;

[0017] The above weight percentage is based on the total components of the thermosetting composition; and

[0018] A thermosetting composition having a viscosity of less than 10,000 cps (more preferably less than 5,000 cps or 2,000 cps, and preferably about 100 to 5,000 cps) at 25°C, measured by a Brookfield rotary disc viscometer using a rotation speed of 5 rpm and a #6 spindle when the solid content is 50% or diluted to 50% solid content prior to the reaction of the above-mentioned di or polyisocyanate.

[0019] 2. In Embodiment 1, the polyamide oligomer is

[0020] 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 a diamine having 4 to 60 carbon atoms having two secondary terminal amine groups (optionally including one other heteroatom) and / or a diamine having 4 to 60 carbon atoms having one or two primary amine groups (optional including one other heteroatom) (preferably the diamine having one or two primary amine groups is characterized as a) a substituent on a carbon atom adjacent to the primary amine nitrogen blocks the nitrogen from forming a strong hydrogen bond with a nearby amide linkage and / or the primary amine nitrogen is a pendant from an aliphatic or aromatic ring structure at a position from the ring such that the primary amine nitrogen cannot form a strong hydrogen bond with a nearby amide linkage) and

[0021] b) a lactone and / or carboxylic acid monomer, wherein the lactone or carboxylic acid unit is derived from an acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms, and said lactone and / or carboxylic acid monomer is a polyamide repeating unit derived by polymerizing a lactone and / or carboxylic acid monomer that forms a repeating unit with a carbonyl from a lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid, which reacts with a primary or secondary amine nitrogen to form an amide linkage to form a polyamide oligomer.

[0022] 3. A thermosetting composition in which, in embodiment 2, at least 40, preferably at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a cyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine and 4,4'-trimethylenedipipiridine, and is part of one or more rings having a nitrogen atom.

[0023] 4. A thermosetting composition in Example 2 or Example 3, wherein at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a diamine having two primary amine groups, and the diamine has two primary amine groups having the following structure.

[0024]

[0025]

[0026] 5. A thermosetting composition in any one of embodiments 2 to 4, wherein the polyamide oligomer is composed of repeating units from a dicarboxylic acid reacted with an amine group, and at least 50, more preferably 80, and preferably at least 90 mol% of the dicarboxylic acid component in the amide repeating unit is a dicarboxylic acid having 10 to 50 carbon atoms, more preferably 25 to 50 carbon atoms.

[0027] 6. A thermosetting composition in any one of embodiments 2 to 5, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is optionally derived from a hydrogenated dimeric fatty acid.

[0028] 7. A thermosetting composition according to prior embodiments 2 to 6, wherein the combined repeating unit of a diamine and a lactone and / or carboxylic acid monomer forming at least one amide link during polymerization into the polyamide is 20 to about 60 weight% of the thermosetting composition.

[0029] 8. A thermosetting composition in any one of embodiments 2 to 7, wherein the combined repeating unit of a diamine and a lactone and / or carboxylic acid monomer forming at least one amide link during polymerization into the polyamide is 25 to about 50 weight% of the thermosetting composition.

[0030] 9. A thermosetting composition in any one of embodiments 2 to 8, wherein at least 90 weight percent of the repeating unit from the diamine is derived from a cyclic and / or dicyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine or 4,4'-trimethylenepiperidine, and the nitrogen atom of the diamine is part of a ring structure.

[0031] 10. A thermosetting composition in any one of embodiments 1 to 9, wherein the reactive polyisocyanate or blocked isocyanate is combined where both are present, and is present in the solution in an amount of about 10 to 50 weight percent of the solution (based on the weight of all components of the composition).

[0032] 11. A thermosetting composition in any one of embodiments 1 to 10, wherein the organic diluent is present in an amount of about 10 to about 50 weight percent of the composition.

[0033] 12. A thermosetting composition according to Example 11, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate.

[0034] 13. A thermosetting composition in any one of embodiments 1 to 12, wherein the solution after evaporation of the solvent is thermosetting.

[0035] 14. A thermosetting composition formed of a self-supporting film, coating, or adhesive in any one of embodiments 1 to 13, or 15 and 16 (below).

[0036] 15. A thermosetting composition in any one of embodiments 1 to 13, wherein the polyisocyanate component has two or more isocyanate groups per polyisocyanate, and the ratio of the isocyanate groups of the polyisocyanate to the combined hydroxyl, amino, and / or carboxyl groups is 2:1 to 1:1.

[0037] 16. A thermosetting composition in any one of embodiments 1 to 13 or 15, wherein, as the organic diluent evaporates, the polyamide oligomer is crosslinked through a reaction with the polyisocyanate component to form a covalent chemical bond by reacting with the hydroxyl, carboxyl and / or amino groups to produce a polymer with a number average molecular weight of at least 1,000,000 g / mol.

[0038] 17. A method for forming a thermosetting coating or film,

[0039] a) a diamine selected from the group consisting of a diamine having 4 to 60 carbon atoms (optionally including 1 other heteroatom) and having 2 secondary terminal amine groups and a diamine having 2 primary amine groups, (the diamine having 2 primary amine groups preferably has the following structure

[0040]

[0041]

[0042] A step of polymerizing by reacting with a carboxylic acid group, - wherein the carboxylic acid unit is derived from a lactone and / or carboxylic acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms; forming a polyamide oligomer by forming a repeating unit with a carbonyl or nitrogen as part of an amide linkage; and said polyamide oligomer has at least two terminal groups selected from amine, carboxyl, or hydroxyl groups -,

[0043] b) optionally heating the polyamide oligomer to a temperature of 100 to 150°C to make it a liquid that is easier to process,

[0044] c) a step of adding one or more non-reactive organic diluents,

[0045] d) a step of adding to the polyamide oligomer about 10 to about 40 weight percent of a polyisocyanate component (optionally having blocked isocyanate group(s)), which reacts with 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 with the reaction of an isocyanate, hydroxyl, or amine group with the carboxyl group, wherein the weight percent of the diamine and carboxylic acid repeating units in the solution is about 10 to about 75 weight percent, the amount of organic diluent is up to 50 weight percent of the solution, the amount of the component reactive with the hydroxyl, carboxyl, and / or amino groups is about 10 to about 40 weight percent of the solution, and at 50% solid content and prior to the reaction of the polyisocyanate, the solution is measured by a Brookfield rotary disc viscometer using a rotation speed of 5 rpm and a #6 spindle, A method comprising a step of having a viscosity of less than 10,000 cps (more preferably less than 2,000 cps and preferably less than 500 cps) at 25℃.

[0046] 18. Method of Example 17, wherein the organic diluent evaporates from the solution and the isocyanate group reacts with a hydroxyl, carboxyl, and / or amino group to form a covalent bond.

[0047] 19. Method of embodiment 18, wherein at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a cyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine or 4,4'-trimethylenedipiperidine, in which the nitrogen atom is secondary and part of the ring.

[0048] 20. In embodiment 18, at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a diamine having two primary amine groups, and the diamine has two primary amine groups of the following structure, method

[0049]

[0050]

[0051] 21. A method in any one of embodiments 17 to 20, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is derived from a dicarboxylic acid having 10 to 50 carbon atoms, more preferably 25 to 50 carbon atoms.

[0052] 22. The method of embodiment 21, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is optionally derived from a hydrogenated dimeric fatty acid.

[0053] 23. A method in any one of embodiments 17 to 20, wherein the component reactive to hydroxyl, carboxyl, 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 said blocked polyisocyanate can be added to a polyamide oligomer without concern for chemical reaction until said blocked isocyanate groups are unblocked.

[0054] 24. A method in any one of embodiments 17 to 23, further comprising a process step of adding to the composition one or more compounds (not polyamides) having a molecular weight of less than 500 g / mol and having three or more groups reactive with an isocyanate selected from the group of amines, carboxyl groups, and hydroxyl groups, in an amount of up to 25 weight%, to facilitate crosslinking of the final composition.

[0055] 25. A method according to embodiment 17, wherein the polyisocyanate is not added until the composition is ready to form a coating or film, and when the polyisocyanate is added to the polyamide oligomer, the polyisocyanate begins to react with the polyamide oligomer through its isocyanate groups.

[0056] 26. As a thermosetting composition,

[0057] a) 10 to 75 weight% of a polyamide oligomer having two terminal groups selected from amine terminal groups, carboxyl terminal groups, and hydroxyl terminal groups,

[0058] b) 10 to about 40 weight percent of a component having two or more reactive oxirane rings (epoxy groups) that react with amines, carboxyl, and / or hydroxyl groups to form covalent chemical bonds,

[0059] Prior to the reaction of the above-mentioned di or polyisocyanate, the composition having two or more reactive oxirane rings when the solid content is 50% or when diluted to 50% solid content, prior to the reaction of the above-mentioned composition having a viscosity of less than 10,000 cps (more preferably less than 5,000 cps, and preferably about 100 to 5,000 cps) at 25°C, measured by a Brookfield rotary disc viscometer using a rotational speed of 5 rpm (revolutions per minute) and a #6 spindle, the component,

[0060] c) optionally one or more non-reactive organic diluents, and

[0061] d) a component having two or more reactive oxirane rings selected from the group consisting of amine, carboxyl, and hydroxyl groups, and one or more compounds having three or more reactive groups, comprising up to 25 weight% of a molecular weight of less than 500 g / mole (not a polyamide); and

[0062] The thermosetting compositions of a), b), c), and d) prior to reaction of the above components having two or more reactive oxirane rings and a terminal group selected from amine, carboxyl, and hydroxyl terminal groups have an average functionality of at least 2.1 per molecule of all oxirane rings for the combined amine, hydroxyl, and carboxyl groups; and

[0063] The above weight percentage is based on the total components of the thermosetting composition.

[0064] 27. In Example 26, the polyamide oligomer is

[0065] 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 a diamine having 4 to 60 carbon atoms having two secondary terminal amine groups (optionally including one other heteroatom) and / or a diamine having 4 to 60 carbon atoms having one or two primary amine groups (optional including one other heteroatom), wherein the diamine having one or two primary amine groups is characterized by a) a substituent on a carbon atom adjacent to the primary amine nitrogen blocks the nitrogen from forming a strong hydrogen bond with a nearby amide linkage and / or the primary amine nitrogen is a pendant from an aliphatic or aromatic ring structure at a position from the ring such that the primary amine nitrogen cannot form a strong hydrogen bond with a nearby amide linkage, and

[0066] b) a lactone and / or carboxylic acid monomer, wherein the lactone and / or carboxylic acid unit is derived from an acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms, and said lactone and / or carboxylic acid monomer is a polyamide repeating unit derived by polymerizing a lactone and / or carboxylic acid monomer that forms a repeating unit with a carbonyl from a lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid, which reacts with a primary or secondary amine nitrogen to form an amide linkage to form a polyamide oligomer.

[0067] 28. A thermosetting composition according to embodiment 27, wherein at least 40, preferably at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a cyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine and 4,4'-trimethylenedipipiridine, where the nitrogen atom is secondary and part of one or more rings.

[0068] 29. A thermosetting composition in which, in embodiment 27, at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a diamine having two primary amine groups, and the diamine has two primary amine groups having the following structure.

[0069]

[0070]

[0071] 30. A thermosetting composition in any one of embodiments 27 to 29, wherein the polyamide oligomer is composed of repeating units from a dicarboxylic acid reacted with an amine group, and at least 50, more preferably 80, and preferably at least 90 mol% of the dicarboxylic acid component that is the amide repeating unit is a dicarboxylic acid having 10 to 50 carbon atoms.

[0072] 31. A thermosetting composition in any one of embodiments 27 to 30, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is optionally derived from a hydrogenated dimeric fatty acid.

[0073] 32. A thermosetting composition in any one of embodiments 27 to 30, wherein the combined repeating unit of a diamine and an acid monomer forming at least one amide linkage during polymerization into the polyamide is 20 to about 60 weight% of the thermosetting composition.

[0074] 33. A thermosetting composition in any one of embodiments 27 to 30, wherein the combined repeating unit of a diamine and an acid monomer forming at least one amide linkage during polymerization into the polyamide is 25 to about 50 weight% of the thermosetting composition.

[0075] 34. A thermosetting composition in any one of embodiments 27 to 30, wherein at least 90 weight percent of the repeating unit from the diamine is derived from a cyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine or 4,4'-trimethylenepiperidine, and the nitrogen atom of the diamine is part of a ring structure.

[0076] 35. A thermosetting composition in any one of embodiments 27 to 30, wherein the organic diluent is present in an amount of about 10 to about 50 weight percent of the composition.

[0077] 36. A thermosetting composition in 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.

[0078] 37. A thermosetting composition in any one of embodiments 26 to 30, wherein, as the solution forms a film or coating by the evaporation of an organic diluent, the polyamide oligomer is crosslinked through a reaction with a component having two or more oxirane rings that react with a hydroxyl, carboxylic acid, and amino group to form a covalent chemical bond, thereby producing a polymer with a number average molecular weight of at least 1,000,000 g / mol.

[0079] 38. A method for forming a thermosetting coating or film,

[0080] a) a diamine selected from the group consisting of a diamine having 4 to 60 carbon atoms having two secondary terminal amine groups (optional including one other heteroatom) and a diamine having two primary amine groups (preferably the diamine has two primary amine groups of the following structure)

[0081]

[0082]

[0083] A step of polymerizing by reacting with a carboxylic acid group, - wherein the carboxylic acid unit is derived from a lactone and / or carboxylic acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms, and forms a polyamide oligomer by forming a repeating unit with a carbonyl or nitrogen as part of an amide linkage; and the polyamide oligomer has at least two terminal groups selected from amine, carboxyl, or hydroxyl groups -,

[0084] b) optionally heating the polyamide oligomer to a temperature of 100 to 150°C to make it a liquid that is easier to process,

[0085] c) a step of adding one or more non-reactive organic diluents, and

[0086] d) a step of adding to a pourable solution at 25°C about 10 to about 40 weight percent of a component having two or more reactive oxirane rings that react with a hydroxyl, carboxyl, 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 the polyamide oligomer, - wherein the weight percent of the diamine and carboxylic acid repeating units in the solution is about 10 to about 75 weight percent, 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 reactive with hydroxyl, carboxyl, and / or amino groups is about 10 to about 40 weight percent of the solution, and at 50% solid content and prior to the reaction of the component having two or more oxirane rings, the solution is a Brookfield rotating disk using a rotation speed of 5 rpm and a #6 spindle. A method comprising having a viscosity of less than 10,000 cps (more preferably less than 2,000 cps and preferably less than 500 cps) at 25°C as measured by a viscometer.

[0087] 39. Method of Example 38, wherein the organic diluent evaporates from the solution and the component having two or more reactive oxirane rings reacts with a hydroxyl group, a carboxylic acid group, and / or an amino group to form a covalent bond.

[0088] 40. A method according to embodiment 38, wherein at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a cyclic diamine having 4 to 15 (more preferably 4 to 13) carbon atoms, such as piperazine or 4,4'-trimethylenedipipiridine, in which the nitrogen atom is a secondary nitrogen group and is part of a ring.

[0089] 41. In embodiment 38, at least 50, more preferably at least 80, and preferably at least 90 mol% of the diamine is a diamine having two primary amine groups, and preferably the diamine has two primary amine groups of the following structure.

[0090]

[0091]

[0092] 42. The method of embodiment 38, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is derived from a dicarboxylic acid having 10 to 50 carbon atoms, more preferably 25 to 50 carbon atoms.

[0093] 43. A method according to embodiment 38, wherein at least 50 weight% (more preferably at least 60, 70, 80 or 90 weight%) of the repeating unit from the carboxylic acid is optionally derived from a hydrogenated dimeric fatty acid.

[0094] 44. A method according to Example 38, wherein a component having two or more reactive oxirane rings and one or more compounds having a molecular weight of less than 500 g / mol in an amount of up to 25 weight% having three or more reactive groups (not polyamides) are added to the composition to facilitate crosslinking of the final composition. Specific details for implementing the invention

[0095] Thermosetting films or thermosetting polymer solutions with a higher proportion of polyamide segments are disclosed for various applications where the strength and / or chemical resistance of polymers having polyether, polyester, or polycarbonate segments is lacking. The solution is useful because the polyamide is formulated to have a sufficiently soft molecular weight to form a solution that can be poured from a beaker at 20 to 50°C with a polymer component (defined as a non-volatile or polymer-forming component) having a solid content of more than 30, 40, 50, 60, 70, or 80 weight% with a complementary amount of volatile solvent (an amount required to make 100 weight% or the total amount together with a non-volatile component).

[0096] The first advantage of this technology is that it has a thermosetting composition rich in polyamide content. In particular, the amide linkages in the thermosetting composition have good resistance to deformation, UV, moisture, etc. It is difficult to develop thermosetting polyamides because more conventional polyamides require relatively high temperatures in the process due to intermolecular hydrogen bonding, aside from other polymers and solvents. By using low molecular weight polyamides, the inventors can improve solvent interactions and promote compatibility with other polymers.

[0097] The first part of the present invention (polyether or polyester segments with a low glass transition point (T gA second advantage of (substitution with polyamide segments) is that polyamide segments tend to promote better wetting and adhesion to various polar substrates, such as glass, nylon, and metals, compared to polyesters or polyether-based polyurethanes. The hydrophobic / hydrophilic properties of polyamides can be adjusted using different ratios of hydrocarbyl moiety to amide linkage. Diamines, diamines, aminocarboxylic acids, and lactones with a large carbon-to-nitrogen ratio tend to be hydrophobic. As the carbon-to-nitrogen ratio in a polyamide decreases, the polyamide becomes more hydrophilic.

[0098] Therefore, polymers prepared with polyamide segments can possess good solvent resistance. Resistance to solvents is desirable for coatings or inks. Solvents can deform the polymer through swelling and apply stress, which may cause the polymer or parts of the polymer to fail prematurely. Solvents can cause the coating to swell and peel off from the substrate at the interface between the two. Adding polyamide to the polymer can increase adhesion to substrates having polar surfaces similar to or compatible with the polyamide.

[0099] One objective of the present patent application is to provide resistance to chain cleavage from hydrolysis and UV-activated chain cleavage by using a high percentage of amide linkages in polymer segments that are selectively incorporated into a thermosetting copolymer of elastomeric properties through reaction with a polyisocyanate or a compound having two or more oxirane rings. Some embodiments may allow some linkages between repeating units to be non-amide linkages. In some embodiments, the linkages between the polyamide oligomer and the isocyanate groups of the polyisocyanate will have a substantial portion of urea linkages. Since urea linkages tend to have a higher melting temperature than urethane linkages, they provide a higher operating temperature. Some embodiments may allow urethane linkages between the polyamide oligomer and the isocyanate groups of the polyisocyanate component when preventing chain cleavage is not a top priority.

[0100] Low T gA significant modification from conventional polyamides to obtain soft polyamide segments is to use one or more of the following: 1) a diamine monomer having a secondary amine terminal group; 2) a diamine having a cyclic ring and steric factor that prevents closed packing of the amide linkage and strong hydrogen bonding; and 3) a) a diamine having one or two primary amine groups characterized by a substituent on a carbon atom adjacent to the primary amine nitrogen that blocks the nitrogen of the amide from forming a strong hydrogen bond with the neighboring amide linkage. An amide linkage formed by a secondary amine and a carboxylic acid-type group is called a tertiary amide linkage. Primary amines react with carboxylic acid-type groups to form secondary amides. The nitrogen atom of the secondary amide has an attached hydrogen atom that often hydrogen-bonds to the carbonyl group of the neighboring amide in the absence of certain types of steric hindrance. Intramolecular H-bonds induce crystallinity with a high melting point and act as crosslinks to reduce chain mobility. When a tertiary amide group is used, the hydrogen on the nitrogen of the amide linkage is removed along with hydrogen bonding. Compared to a hydrogen-attached secondary amide group, a tertiary amide bond with one additional alkyl group attached exhibits reduced polar interactions with neighboring amide groups when the polymer is present in bulk polymer samples. Reduced polar interactions mean that the glassy or crystalline phase containing the amide linkage generally melts at lower temperatures than similar amide groups, which are secondary amide groups. One method of supplying secondary amine reactants, which serve as precursors for tertiary amide linkages, is to substitute the nitrogen atoms(s) of the amine-containing monomer with alkyl groups. Another method of supplying 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 nitrogen on both sides is of the secondary type and is part of a heterocyclic ring.

[0101] The crosslinkable or thermosetting composition of the present disclosure is preferred because it has a high weight percentage of polyamide repeating units in a polyamide oligomer, a reasonable amount of a component capable of chemically reacting with the terminal groups of the polyamide oligomer to form a thermosetting composition (often an epoxy compound of the type having two or more oxirane rings capable of reacting with Zerewitinoff groups or a polyisocyanate), and, if necessary, an amount of solvent sufficient to lower the viscosity of the thermosetting composition to a pourable composition at 20 to 30°C and a solvent capable of forming a coating or film at 20, 25, or 30°C without excessive difficulty.

[0102] In one embodiment, the amide-type repeating unit comprises a diamine (wherein the amine terminal group reacts with a carboxylic acid to form an amide bond as described below, and the carboxylic acid component reacts with the amine to form an amide). The polyamide oligomer may include repeating units other than the amide-type repeating unit, but the intention is to use most of the amide-forming repeating units in the polyamide oligomer.

[0103] The amount of amide forming repeating units in the thermosetting composition (including solvent, if present) is about 10 or 15 to about 75 weight% of the thermosetting composition, more preferably about 15 or 20 to about 60 weight%, preferably about 15, 20 or 25 to about 50 weight%. The amount of component reactive with polyamide oligomers (often polyisocyanates and sometimes blocked isocyanate compounds) is about 10 to about 50 weight% of the thermosetting composition, more preferably about 10 to about 40 weight%, preferably about 15 to about 35 weight%. The amount of solvent is preferably up to 60 weight% of the thermosetting composition, more preferably 10 to 60 weight% of the composition, more preferably 10 to 50 weight% of the composition, preferably about 10 to 30 weight%. Optionally, low molecular weight components that are difunctional or trifunctional or higher (preferably trifunctional or higher, may be present in up to 15 weight percent of the thermosetting composition) are present. The thermosetting composition may also include conventional amounts of pigments, conventional amounts of adhesives, fillers, biocides, film reinforcing agents, film surface modifiers (e.g., gloss reducers), and other components conventionally used in coatings, inks, and films.

[0104] Since the inventors desire thermosetting properties, the polyamide will generally have reactive terminal groups at both ends. The reactive groups may be Zerevitinov groups, such as hydroxyl and / or amine groups. Additionally, in some embodiments, the polyamide may be carboxylic acid terminated. The carboxylic acid may react directly with the polyepoxide to form a high molecular weight reaction product (a chain extended into the polyepoxide). The carboxylic acid-terminated polyamide may promote the decomposition of the isocyanate group (from the polyisocyanate component) to release one molecule of CO2 and an amine group (a known reaction between the isocyanate and carboxylic acid groups). Subsequently, the amine generated from the isocyanate group may react with the carboxylic acid group or additional isocyanate group (if present) on the polyamide. The overall result is that the carboxylic acid-terminated polyamide can be reacted into a higher molecular weight or crosslinking reaction product. In a preferred embodiment, the terminal group of the polyamide is an amine or hydroxyl terminal group to avoid the generation of CO2. An amine (primary or secondary) terminal group can be achieved by using a molar excess of the diamine component relative to the carboxylic acid component in the manufacture of the polyamide. Hydroxyl terminal groups can be introduced in various ways. One method is to initially form an amine-terminated polyamide and then react the polyamide with a hydroxyl carboxylic acid having 3 to 30 carbon atoms or a lactone having 2 to 10 (or 4 to 10) carbon atoms. A single unit is obtained from the hydroxycarboxylic acid or lactone when the molar amount of the carboxyl functional group in the hydroxycarboxylic acid and / or lactone is equal to the number of terminal amine groups. When a molar excess of the hydroxycarboxylic acid and / or lactone is used, a short polyester segment is developed as part of the polyamide. In addition, a carboxylic acid-terminated polyamide can be produced and reacted with an amino alcohol having 2 to 20 carbon atoms to convert the carboxylic acid group into a hydroxyl group.

[0105] Sometimes, carboxylic acid-terminated telechelic polyamide segments are N-methylaminoethanol or HN(R α )(R β It is functionalized by reacting with amino alcohols such as ), where R α is a C1 to C4 alkyl group and R β is an alcohol group and C2 to C 12 Contains alkylene, and alternatively R α and R β C3 to C6 are interconnected and contain a ring structure and a pendant hydroxyl group (as in 2-hydroxymethylpiperidine). 16 An alkylene group can be formed, and one of the two can produce a telechelic polyamide having a terminal hydroxyl group. The reaction of a secondary amine (opposite to the hydroxyl group) and a carboxylic acid may be preferred by using a 100% molar excess of amino alcohol and carrying out the reaction at 160°C + / - 10 or 20°C. The excess amino alcohol can be removed by distillation after the reaction.

[0106] In embodiments using blocked isocyanate groups, the polyisocyanate may be added to other components (e.g., a solvent, a polyamide, and an optional crosslinking compound having three or more Zerewittinov groups) and packaged for shipment to the end user. When conventional unblocked polyisocyanates are used with polyamides and solvents, the unblocked polyisocyanate is not added until immediately before use of the coating, adhesive, or ink. The unblocked isocyanate groups react rapidly with the present Zerewittinov groups (depending on temperature and the presence of any catalyst for urethane formation). An optional urethane-forming catalyst may also be present in the formulation with either the blocked or unblocked polyisocyanate. These catalysts for urethane formation are known in the art.

[0107] The polyamide, solvent, and other polymer-forming components (typically present in a solid content of 50% or more) will have a viscosity of less than 10,000 cps, more preferably less than 5,000 cps, and in some embodiments less than 2,000 or 500 cps, more preferably about 100 to 5,000 cps (when measured at 50 wt% solid content) as measured by a Brookfield circular disc viscometer (e.g., Model LV, RV, HA, or HB, where the designation indicates four basic spring torques) having a circular #6 disc rotating at 25°C and 5 rpm. The composition may be diluted with more solvent if the solid content is initially greater than 50% for the purpose of measuring the viscosity and determining whether the viscosity is within the required range. This type of viscosity facilitates the application of the material to a substrate by facilitating the pouring of the polyamide into the solvent from a 1-gallon paint can or other container at 25°C.

[0108] The term polyamide oligomer refers to an oligomer having two or more amide links, or sometimes the amount of amide links will be specified. Generally, a polyamide oligomer will have at least one diamine component and at least one diacid component or at least two hydroxycarboxylic acid and / or lactone components (to form at least two amide links). As shown in the examples, the polyamide generally has 1 to 20, more preferably 1 to 10 diamines per polyamide oligomer.

[0109] The inventors will define polyamide oligomers as species having two or more amide links per oligomer and a number average molecular weight of less than 5,000 g / mol (e.g., often less than 2,500 or 2,000 g / mol). Generally, polyamides will have a number average molecular weight of at least 300 and more preferably at least 400 g / mol.

[0110] Generally, amide linkages are formed from the reaction of a carboxylic acid group and an amine group or from the ring-opening polymerization of lactones (e.g., when an ester linkage in a ring structure is converted to an amide linkage in a polymer having a terminal hydroxyl group). As previously noted, multiple repeating units from lactones can be added to polyamides by the ring-opening polymerization of lactones. The formation of amides from the reaction of a carboxylic acid group and an amine group can be catalyzed by boric acid, boric acid esters, boranes, phosphoric acid, phosphates, phosphate esters, amines, acids, bases, silicates, and silsesquioxanes. Additional catalysts, conditions, etc. are available in literature such as ["Comprehensive Organic Transformations" by Larock].

[0111] The polyamides of the present disclosure may contain small amounts of ester linkages, ether linkages, urethane linkages, urea linkages, etc., where additional monomers used to form these linkages are useful for the intended use of the polymer. This allows other monomers and oligomers to be included in the polyamide, thereby providing certain properties that are required but cannot be achieved with 100% polyamide segment oligomers. Sometimes, added polyethers, polyesters, or polycarbonates result in softer (lower T) g It provides a segment. Sometimes, it is desirable to convert the carboxyl terminal group or the primary or secondary amine terminal group of the polyamide into other functional terminal groups capable of condensation polymerization.

[0112] Desirable amide or tertiary amide-forming monomers include dicarboxylic acids, hydroxycarboxylic acids, lactones, diamines, aminocarboxylic acids, and lactams.

[0113] A preferred dicarboxylic acid is a cyclic, linear, or branched (optionally containing aromatic groups) alkylene having 2 to 48 carbon atoms, wherein the alkylene portion of the dicarboxylic acid optionally contains up to one heteroatom per 2 carbon atoms (or one heteroatom per 10 carbon atoms), more preferably 8 to 38 carbon atoms (the acid will contain 2 more carbon atoms than the alkylene portion or 4 to 50 carbon atoms and more preferably 10 to 40 or 10 to 50 carbon atoms and in some embodiments 25 to 50 carbon atoms). These include dimeric fatty acids, hydrogenated dimeric acids, sebacic acids, etc. Generally, the inventors prefer acids having larger alkylene groups, which are generally T g This is because it provides polyamide repeating units with lower values. Hydrogenation of dimeric fatty acids makes them less reactive later through the removal of carbon-carbon double bonds by hydrogenation.

[0114] A preferred hydroxycarboxylic acid will have 3 to 30 carbon atoms and more preferably 5 to 8 carbon atoms. A preferred lactone will have 2 to 10 (or 4 to 10) carbon atoms and preferably 5 to 8 carbon atoms.

[0115] A preferred diamine has 60 or fewer carbon atoms and optionally includes one heteroatom (in addition to two nitrogen atoms) for each of the three carbon atoms of the diamine (or one heteroatom (in addition to two nitrogen atoms) for each of the ten carbon atoms), and optionally includes various cyclic, aromatic, or heterocyclic groups, provided that one or both of the amine groups are secondary amines; and a preferred chemical formula is as follows.

[0116]

[0117] In the above equation, Rb is a direct bond or a linear or branched alkylene group of 2 to 36 carbon atoms and more preferably 2 to 12 (or 4 to 12) carbon atoms (optionally containing or having a cyclic, heterocyclic, or aromatic portion) (optional containing up to 1 heteroatom (or 3 heteroatoms per 10) carbon atoms of the diamine); and R c and R d is individually a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 (or 2 to 4) carbon atoms; or R c and R d are connected 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 them is R in the carbon atom b Connected to, and more desired is R c and R d is 1 to 4 (or 2 to 4) carbon atoms. This diamine is N,N'-bis(1,2,2-trimethylpropyl)-1,6-hexanediamine, Albermarle's Ethacure TM 90; Clearlink TM 1000 or Jefflink TM 754 (both products of Huntsman); N-methylaminoethanol; dihydroxy-terminated, hydroxyl and amine-terminated, or diamine-terminated poly(alkylene oxide) having 2 to 4 carbon atoms in the alkylene and a molecular weight of 100 to 2000; N,N'-diisopropyl-1,6-hexanediamine; N,N'-di(sec-butyl)phenylenediamine; piperazine; homopiperazine; and methyl-piperazine. Jefflink TM The 754 has the following structure and

[0118]

[0119] And ClearlinkTM 1000 has the following structure

[0120]

[0121] In one embodiment, the diamine is HNR 1 -CHR 2 -X-CHR 3 -NR 4 H, where X is a hydrocarbon or a direct bond having 0 to 34 carbon atoms, and R 1 , R 2 , R 3 and R 4 is H, the following alkyl group, or the following alkylene bridge group, and four substituents R 1 , R 2 , R 3 and R 4 At least two of them are alkyl groups having 1 to 4 carbons or R 1 , R 2 , R 3 and R 4 It forms a 5 to 7-membered hydrocarbon ring as part of an alkylene bridge between the connection points for two selected substituents.

[0122] Another diamine with an aromatic group is N,N'-di(sec-butyl)phenylenediamine, refer to the structure below:

[0123]

[0124] In one embodiment, the preferred diamine is a diamine in which two amine groups are secondary amines.

[0125] Suitable lactams include a ring structure without substituents on the nitrogen of the lactam having a total of 5 to 13 carbon atoms (if carbonyl is included), and a straight-chain or branched alkylene segment of 4 to 12 carbon atoms within it such that the substituent on the nitrogen of the lactam (if the lactam is a tertiary amide) is an alkyl group of 1 to 8 carbon atoms and more preferably an alkyl group of 1 to 4 carbon atoms. Dodecyl lactams, alkyl-substituted dodecyl lactams, caprolactams, alkyl-substituted caprolactams, and other lactams having larger alkylene groups are those that have a lower T g It is a preferred lactam because it provides repeating units having a value. The aminocarboxylic acid has the same number of carbon atoms as the lactam. Preferably, the number of carbon atoms in the linear or branched alkylene group between the amine and the carboxylic acid group of the aminocarboxylic acid is 4 to 12, and the substituent on the nitrogen of the amine group (in the case of 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. An aminocarboxylic acid having a secondary amine group is preferred.

[0126] In one embodiment, preferably at least 50 weight%, more preferably at least 60, 70, 80, or 90 weight% of the polyamide oligomer comprises repeating units from diamines and diamines having a repeating unit structure as follows.

[0127]

[0128] In the above equation, R a is the alkylene portion of a dicarboxylic acid and is a cyclic, linear, or branched (optional aromatic group-containing) alkylene having 2 to 48, more preferably 8 to 38 carbon atoms, optionally containing up to 1 heteroatom per 3 carbon atoms of the acid (or 1 heteroatom per 10 carbon atoms), (the acid will contain 2 more carbon atoms than the alkylene portion of the acid); and Rb is a directly bonded or linear or branched alkylene group of 2 to 36 or 2 to 60 carbon atoms and more preferably 2 to 12 or 4 to 12 carbon atoms (optionally cyclic, heterocyclic, or aromatic moiety(s) or containing the same) (optional containing up to 1 heteroatom per 10 carbon atoms (or 3 heteroatoms per 10 carbon atoms)); and R c and R d is individually a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 (or 2 to 4) carbon atoms; or R c and R d are connected 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 them is R in the carbon atom b Connected to, and more desired is R c and R d It is an alkylene group consisting of 1 to 4 (or 2 to 4) carbon atoms.

[0129] In one embodiment, preferably at least 50 weight%, or at least 60, 70, 80, or 90 weight% of the telechelic polyamide or said polyamide oligomer comprises repeating units from a lactam or aminocarboxylic acid having the following structure.

[0130]

[0131] In the above formula, the repeating unit may exist in various orientations in oligomers derived from lactams or aminocarboxylic acids depending on the initiator type, where each R e is independently a linear or branched alkylene having 4 to 12 carbon atoms, and each R f is independently a linear or branched alkyl of 1 to 8 (more preferably 1 to 4) carbon atoms.

[0132] The polyamides described above are useful for preparing solutions with polyisocyanates. Polyisocyanates will be used herein to refer to isocyanates containing species having two or more isocyanate groups per molecule. Preferably, polyamides have terminal groups that are reactive with isocyanates to form urea linkages and / or urethane linkages. Groups that are chemically reactive with isocyanates to form chemical bonds are known as Zerevitinov groups and include primary and secondary amines and primary and secondary alcohols. The nitrogen of the primary or secondary amine binds to the carbonyl group of the isocyanate, and the hydrogen from the primary or secondary amine moves from the amine and binds to the NH group of the isocyanate. The oxygen of the primary or secondary alcohol binds to the carbonyl group of the isocyanate, and the hydrogen from the hydroxyl group of the alcohol moves and binds to the NH group of the isocyanate.

[0133] In the second embodiment, the preferred diamine is a specific diamine having a specific structure shown below that produces a polyamide soluble at 20 to 30°C, which can form the basis of a pourable thermosetting liquid composition at 20 to 30°C and a reasonable solvent content. In the third embodiment, the preferred diamine is a combination of a secondary amine terminal group and an amine combined with a specific primary diamine shown below that also produces a polyamide soluble at 20 to 30°C, which can form the basis of a pourable thermosetting liquid composition.

[0134] The following are examples of aliphatic, alicyclic, and aromatic diamines having primary amine terminal groups that produced soluble polyamides when reacted with aliphatic diacids such as sebacic acid and / or dimeric fatty acids. Although we do not wish to be bound by theory, when depicted with appropriate bond angles and bond lengths and stereo-bulky ring structures, their substantially non-linear structures produce polyamides that are significantly non-linear, cannot adhere closely to each other, and cannot be easily rearranged to strengthen hydrogen bonds to adjacent or nearby amide linkages; therefore, these polyamines and similar polyamines are considered to provide an opportunity for compatible polar solvents to provide solubilization at temperatures between 10 and 150°C.

[0135]

[0136]

[0137] Additionally, two other diamines have been found to tend to form solvent-compatible polyamides useful as components in the present disclosure. These are 1,5-diamino-2-methylpentane and 4,4'-trimethylenedipipiridine. The structures for these molecules are shown below.

[0138]

[0139] The following are examples of aliphatic, alicyclic, and aromatic diamines that did not produce soluble polyamides when reacted with aliphatic diacids, such as sebacic acid and / or dimeric fatty acids. Although we do not wish to be bound by theory, it is believed that when drawn with appropriate bond angles and bond lengths, their substantially linear structures produce polyamides that are considerably linear, can be closely bonded to each other, and can hydrogen bond to adjacent or nearby amides, thereby minimizing the opportunity for compatible polar solvents to provide solubilization at temperatures between 10 and 150°C.

[0140]

[0141] It is also acknowledged that the molecular weight of a polyamide section is often controlled by using an excess of one component to form the terminal end group of the component used in excess (compared to the diamine component), such as a diamine component that can be used in excess to form an amine-terminated polyamide section with a controlled molecular weight that is lower than would have been achieved if a 1:1 stoichiometry between the amine group and the carboxylic acid group had been used. The amine-terminated polyamide reacts with a polyisocyanate to form a urea linkage (which generally has a higher softening temperature than the linkage formed between the hydroxyl group and the polyisocyanate). Accordingly, in some examples, the inventors reacted an amine-terminated oligomer with caprolactone to form a hydroxyl-terminated polyamide (which has a slightly lower softening temperature). Additional caprolactone units can be added to the hydroxyl terminal group to form an oligomer from the ring-opening caprolactone repeating unit onto the polyamide oligomer. Having polycaprolactone segments helps soften the composition and lower the softening temperature of polyamide-rich oligomers.

[0142] The manufacturing process of the polyamide is optimized to produce a waxy solid telechelic polyamide-rich polymer at room temperature that can be melted without a solvent at a temperature of 100 to 140°C, more preferably 110 to 130°C and preferably 120 to 130°C, forming a liquid telechelic polyamide-rich oligomer that can be blended with a compound reactive to the terminal groups of the telechelic oligomer (Zerewitinov groups and 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 a compound reactive to the telechelic end group), a solvent is added to convert the polyamide-rich composition into an easily stirred liquid (viscosity of less than 10,000 or 5,000 cps at 50 wt% solids using a rotary disc / spindle viscometer with a rotation speed of 5 rpm and a #6 spindle at 25°C, less than 2,000 or 500 cps in some embodiments, more preferably about 100 to 5,000 cps).

[0143] Solvents useful for the present disclosure are those having a boiling point at 1 atm at 40 to 120°C and having 2 to 10 carbon atoms, one or more oxygen atoms, and one or more hydrogen atoms. Compounds used as solvents in the examples include isopropanol, acetone, dimethyl carbonate, and butyl acetate.

[0144] Suitable polyisocyanates include aliphatic, alicyclic, aliphatic, aromatic aliphatic, aromatic, and heterocyclic polyisocyanates, as well as their oligomerization products, which have an average of about 2 or more isocyanate groups per molecule, preferably an average of about 2 to about 4 isocyanate groups, used alone or as a mixture of two or more. Diisocyanates are more preferred.

[0145] Specific examples of suitable aliphatic polyisocyanates include alpha, omega-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, 2-methyl-1,5-pentamethylene diisocyanate, etc. Polyisocyanates having fewer than 5 carbon atoms may 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.

[0146] Specific examples of suitable cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate (from Bayer Corporation, Desmodur TM (commercially available as), isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis-(isocyanatomethyl)cyclohexane, etc. Preferred alicyclic polyisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

[0147] Specific examples of suitable aromatic aliphatic polyisocyanates include m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, etc. A preferred aromatic aliphatic polyisocyanate is tetramethylxylylene diisocyanate.

[0148] 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.

[0149] Examples of suitable heterocyclic isocyanates include 5,5'-methylenebisfurfuryl isocyanate and 5,5'-isopropylidenebisfurfuryl isocyanate.

[0150] In some embodiments of the present invention, a blocked isocyanate reactant is used to minimize the reaction of the isocyanate group and the increase in intrinsic viscosity up to a precise time that allows for an increase in the molecular weight of the reactant. Blocked isocyanate groups are well known in the art, and compounds having blocked isocyanate groups are commercially available, and at least one blocked isocyanate compound is presented in the examples. Generally, the blocked isocyanate group is thermally unblocked by heating the reactant. Some blocked isocyanate compounds have used ketoxime chemistry described in the literature and known.

[0151] In some embodiments, low molecular weight polyols and / or polyamines are used to provide "chain extension" and / or "crosslinking" of a reaction mixture containing an isocyanate-terminated reactant or a polyisocyanate. Examples include low molecular weight polyols and polyamines with a number average molecular weight of about 500 daltons or less. In this context, "polyol" refers to any product having an average of about 2 or more hydroxyl groups per molecule. In this context, "polyamine" is used to describe a compound having two or more primary or secondary amine groups capable of reacting with an isocyanate group to form a urea linkage. Specific examples include aliphatic, alicyclic, 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, alicyclic, and aromatic polyamines having 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms, such as ethylenediamine and similar alkylene di and triamines, in particular diamines and triamines. Polyamines may include compounds formed by the reaction of hydrazine with an acid, such as hydrazine and adipic acid dihydrazide. Low molecular weight compounds are preferred because they move through the composition more rapidly than oligomeric or polymeric species. Any other compound known to function as a chain extender in polyester polyols and polyamides may also be used.

[0152] In some embodiments, trifunctional isocyanate compounds and higher isocyanate-functional polyisocyanates may be used. Sometimes these are formed by trimming low-functional diisocyanates, or sometimes by reacting di and / or tri-isocyanates with triols, tetrahydric alcohols, and highly functional alcohols. They may also be prepared by reacting triamines and highly functional amines with di and / or triisocyanates. Other polyfunctional isocyanate compounds may be prepared by three or more functional amines and by traditional reactions that convert amine groups into isocyanate groups.

[0153] A preferred epoxy resin is a liquid resin based on a bisphenol compound, particularly bisphenol A, bisphenol F, or bisphenol A / F, as is available from Dow, Huntsman, and Hexion. This liquid resin has low viscosity compared to epoxy resins and has good properties as a coating when fully cured. They may optionally exist in combination with a bisphenol A solid resin or a bisphenol F novolak epoxy resin.

[0154] In addition, suitable as epoxy resins are saturated or unsaturated, branched or unbranched, cyclic or open-chain C2 to C2 compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, or dibromo-neopenyl glycol. 30These are glycidyl ethers of diols, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, or glycerol, as well as trifunctional or tetrofunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyols such as alkoxylated glycerol or alkoxylated trimethylolpropane, aliphatic or alicyclic polyepoxides such as glycidyl ethers of diols; hydrogenated bisphenol A, F, or A / F liquid resins, or glycidylation products of hydrogenated bisphenol A, F, or A / F; N-glycidyl derivatives of amides or heterocyclic nitrogen bases such as triglycidyl cyanurate and triglycidyl isocyanurate, as well as reaction products from epichlorohydrin and hydantoin.

[0155] Finally, other suitable epoxy resins are epoxy resins derived from the oxidation of olefins, for example, vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadien, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene, or divinylbenzene.

[0156] 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 monovalent or polyvalent phenols and aliphatic or alicyclic alcohols.

[0157] Other additives known to those skilled in the art may be used to aid in the preparation of the thermosetting compositions of the present invention. Such additives include surfactants, stabilizers, defoaming agents, flash rust inhibitors, adhesion promoters, adhesives, surface tension modifiers, plasticizers, thickeners, leveling agents, antimicrobial agents, fungicides, antioxidants, UV absorbers, slip modifiers, flame retardants, pigments, fillers, dyes, etc. These additives are known in the art and may be added at any stage of the manufacturing process. They will all be used in conventional amounts for conventional purposes in coatings and adhesives.

[0158] As a coating composition or adhesive, the composition of the present disclosure may 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. These will protect the substrate from various environmental substances such as water, chemicals, corrosive substances, dust, ozone, soot, etc., and provide a surface that is easy to clean.

[0159] The compositions of the present invention and their formulations are useful as self-supporting films, coatings on various substrates, or adhesives having a longer effective life than similar polyurethane compositions or other improved properties.

[0160] Example:

[0161] Definition of reactants

[0162] H-Dimeric Fatty Acid- (Generally hydrogenated dimers formed from conventional fatty acids (molecular weight approximately 565 g / mol)

[0163] Piperazine-Piperazine (molecular weight approx. 86 g / mol)

[0164] Caprolactone - Caprolactone (approx. 114 g / mol)

[0165] Sebacic acid-1,8-octane dicarboxylic acid (approx. 202 g / mol)

[0166] DMDC-4,4'-Methylenebis(2-methylcyclohexylamine), (molecular weight approx. 238.4 g / mol)

[0167] mPDA- meta-phenylenediamine (molecular weight approx. 86 g / mol)

[0168] Verstanat TM B 1186 A - 60 wt% blocked isocyanate in naphtha, 7.1 NCO content, aliphatic, obtained from Evonik, the blocking agent may be ε-caprolactam.

[0169] Desmodur TM5375- 4,4'-Methylene dicyclohexyl diisocyanate (molecular weight approximately 262.35 g / mol available from Covestro).

[0170] Desmodur TM N3600- Hexamethyl diisocyanate (HDI) trimer available from Covestro.

[0171] Trimethylolpropane-trimethylolpropane

[0172] DBE - A mixture of dimethyl adipate, dimethyl glutarate, and dimethyl succinate; CH3O2C(CH2) available from Sigma Aldrich n CO2CH3(n=2,3,4).

[0173] DMC - Dimethyl Carbonate

[0174] Xylene-xylene

[0175] Acetone-acetone

[0176] Butyl acetate-butyl acetate

[0177] Polyamide synthesis

[0178] Diamine and diacid monomers are added to the reactor. The reactor is flushed with nitrogen and maintained under an inert atmosphere. The reactor is heated to 160°C and maintained at that temperature for 2 hours, then further heated to 200°C and maintained at that temperature for 48 hours or until the acid value inside the reactor drops below 1 (mgKOH / g). Water is formed during the reaction, which causes it to distill out of the reactor. Subsequently, the reactor is cooled to 180°C and another monomer is 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 of 100°C or higher.

[0179]

[0180] Procedure for (one component baked using a blocked isocyanate polyamide coating):

[0181] Polyamide polyol was melted at 130°C, and high-boiling point solvents (DBE and butyl acetate) were added to the melt to dilute the polyol. Subsequently, the solution was cooled to 60°C, and other components were added. Then, the solution was 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 it at a suitable temperature (80°C) for 10 minutes, and then baking it at 150°C for 30 minutes.

[0182]

[0183]

[0184]

[0185] Procedure for bicomponent (polyamide polyol and polyisocyanate) solvent-based coating:

[0186] The polyamide polyol was melted at 130°C, and high-boiling point solvents (DBE and butyl acetate) were added to the melt to dilute the polyol. Subsequently, the solution was cooled to 60°C, and an extender and DBTL catalyst were added to the solution. Then, the solution was further cooled to room temperature. The resulting solvent-based polyol solution is a low-viscosity liquid. A coating was first prepared by mixing the polyol solution component and the isocyanate component at room temperature, and then the film was cast onto a substrate. The film was dried at room temperature 7 days prior to the test.

[0187]

[0188]

[0189]

[0190] In the following examples: the hydroxyl (OH) value was determined using the TSI method (ASTM E1899); the acid value was determined by titration using NaOH titrant and methylene blue indicator; and, as understood by those familiar with the use of viscometer instruments, the viscosity was measured by a Brookfield DV-E viscometer using an LV spindle at 60 rpm or 30 rpm depending on how viscous the material was.

[0191] Example 1 (Polyamide Synthesis): 750 parts of hydrogenated dimeric acid were mixed with 221 parts of meta-phenylenediamine under a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and allowed to evaporate from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. Then, 166 parts of epsilon-caprolactone were 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.

[0192] Example 2 (Polyamide Synthesis): 750 parts of hydrogenated dimeric acid were mixed with 164 parts of piperazine under a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and allowed to evaporate from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. Then, 134 parts of epsilon-caprolactone were added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a bright yellow product with an OH value of 65.9 and a melt viscosity of 3,100 cP at 100°C.

[0193] 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 under a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and allowed to evaporate from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. The resulting polymer was a bright yellow product with an OH value of 65.8 and a melt viscosity of 650 cP at 100°C.

[0194] Example 4 (Polyamide Synthesis): 620.5 parts of hydrogenated dimeric acid were mixed with 285.5 parts of isophoronediamine under a nitrogen atmosphere and heated to 180°C. As the monomers began to react, water was formed and allowed to evaporate from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. Then, 134 parts of epsilon-caprolactone were added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a bright yellow product with an OH value of 65.9 and a melt viscosity of 19,000 cP at 100°C.

[0195] Example 5 (Polyamide Synthesis): 509.2 parts of hydrogenated dimeric 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 allowed to evaporate from the reactor. After 48 hours, the acid value of the mixture was less than 1 mg KOH / g. Then, 152.1 parts of epsilon-caprolactone were added to the reactor and reacted at 180°C for 12 hours. The resulting polymer was a bright yellow product with an OH value of 74.5 and a melt viscosity of 15,000 cP at 100°C.

[0196] Example 6: 128 g of propylene glycol monomethyl ether acetate was combined with 10.5 g of Lubrizol Solsperse® M387 polymer dispersant and 30 g of BASF Laropal® A81 aldehyde resin, and then mixed at 500 RPM until homogeneous. 392 g 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 together 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 then 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed at 500 RPM for 10 minutes.

[0197] Example 7: 73 g of propylene glycol monomethyl ether acetate was combined with 6 g of Lubrizol Solsperse® M387 polymer dispersant, 17 g of BASF Laropal® A81 aldehyde resin, and 2.5 g of BYK-052 N silicone-free defoamer, and then mixed at 500 RPM until homogeneous. 224 g of rutile titanium dioxide was added and mixed at 1500 RPM using a coilless blade until a 7+ Hegman grind was obtained using a Hegman gauge. 320 g of the polyamide of Example 2 was added together 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, and then mixed at 500 RPM for 15 minutes. 192 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0198] Example 8: 128 g of propylene glycol monomethyl ether acetate was combined with 10.5 g of Lubrizol Solsperse® M387 polymer dispersant and 30 g of BASF Laropal® A81 aldehyde resin, and then mixed at 500 RPM until homogeneous. 392 g of rutile titanium dioxide was added and mixed at 1500 RPM using a coilless blade until a 7+ Hegman grind was obtained. 196 g of the polyamide from Example 3 was added together with 140 g of methyl ethyl ketone and 0.45 g of dibutyltin dilaurate, and then mixed at 500 RPM for 15 minutes. 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0199] Example 9: 128 g of propylene glycol monomethyl ether acetate was combined with 10.5 g of Lubrizol Solsperse® M387 polymer dispersant and 30 g of BASF Laropal® A81 aldehyde resin, and then mixed at 500 RPM until homogeneous. 392 g of rutile titanium dioxide was added and mixed at 1500 RPM using a coilless blade until a 7+ Hegman grind was obtained. 196 g of Asahi Masei Duranol® T5652 polycarbonate was added together with 140 g of methyl ethyl ketone and 0.45 g of dibutyltin dilaurate, and then mixed at 500 RPM for 15 minutes. 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0200] Example 10: 128 g of propylene glycol monomethyl ether acetate was combined with 10.5 g of Lubrizol Solsperse® M387 polymer dispersant and 30 g of BASF Laropal® A81 aldehyde resin, and then mixed at 500 RPM until homogeneous. 392 g of rutile titanium dioxide was added and mixed at 1500 RPM using a coilless blade until a 7+ Hegman grind was obtained. 196 g of Panolam Piothane® 67-2000 HNA polyester polyol was added together with 140 g of methyl ethyl ketone and 0.45 g of dibutyltin dilaurate, and then mixed at 500 RPM for 15 minutes. 98 g of Covestro Desmodur® N-3600 aliphatic polyisocyanate was added and mixed for 10 minutes.

[0201] The compositions of Examples 6 to 10 were coated onto cold-rolled steel according to ASTM D523-08. In the examples listed in Table 6 below, the initial viscosity ("IV") was determined at 100 RPM using ASTM D4287-10, spindle #3, the average 60° gloss ("Gloss") was determined using ASTM D523-08, the average 60° haze ("Haze") and average 60° distinction ("DOI") of the image were determined using ASTM D4039-09, the average 7-day Koenig hardness ("Hardness") was determined using ASTM D4366, the flexibility ("Flex") was determined using ASTM D522-13, the impact (direct / reverse) ("Impact") was determined using ASTM D2794-93, and the average 1-day wet crosshatch adhesion ("Adhesion") was determined using ASTM D3359-17.

[0202]

[0203] Except as otherwise indicated in the Examples or elsewhere, all numerical quantities specifying amounts, reaction conditions, molecular weights, number of carbon atoms, etc. in this Detailed Description are understood to be modified by the word "about." Unless otherwise indicated, all percentage and formulation values ​​are on a molar basis.

[0204] Unless otherwise indicated, all molecular weights are number average molecular weights. Unless otherwise indicated, each chemical or composition referred to herein shall be interpreted as a commercial-grade material, and such material may contain isomers, byproducts, derivatives and other such materials, which are understood to be present in the commercial grade.

[0205] As used herein, the expression “essentially composed of” allows for the inclusion of a material that does not specifically affect the basic and novel features of the composition under consideration. All embodiments of the invention described herein may be considered and read from both an open and comprehensive perspective (i.e., using the word “comprises of”) and a closed and exclusive perspective (i.e., using the word “composed of”).

[0206] Parentheses used herein are used to 1) optionally mean monomer(s) mean monomer or monomers, or (meth)acrylate means methacrylate or acrylate, 2) to quantify or further define previously mentioned terms, or 3) to enumerate narrower embodiments.

[0207] Although specific representative embodiments and details have been presented for the purpose of illustrating the 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 invention.

Claims

Claim 1 A thermosetting composition comprising: a) 10 to 75 weight% of a polyamide oligomer mainly having two terminal groups selected from amine, hydroxyl, or carboxylic acid terminal groups and at least two amide linkages; b) 10 to 50 weight% of a di or polyisocyanate component that reacts with amine, carboxyl, and / or hydroxyl groups to form a covalent chemical bond (optionally, when isocyanate reactivity is temporarily blocked); c) one or more non-reactive organic diluents; and d) one or more compounds having a molecular weight of less than 500 g / mole in an amount of up to 50 weight%, having three or more groups reactive with an isocyanate selected from the group of amines and hydroxyl groups; wherein, prior to the reaction of the isocyanate group with the terminal group selected from amines, hydroxyl, or carboxylic acid terminal groups, the thermosetting compositions of a), b), c), and d) have an average functionality of at least 2.1 per molecule of all isocyanates, amines, hydroxyl, and carboxylic acid terminal groups; said weight percentages are based on the total components of the thermosetting composition; and prior to the reaction of the di or polyisocyanate, the composition has a viscosity of less than 10,000 cps at 25°C, measured by a Brookfield rotary disc viscometer using a rotation speed of 5 rpm and a #6 spindle when the solid content is 50% or diluted to 50% solid content. Claim 2 In claim 1, the polyamide oligomer comprises: a) a diamine having two amine groups capable of forming a covalent bond with a carbonyl of a carboxylic acid selected from the group consisting of a diamine having 4 to 60 carbon atoms having two secondary terminal amine groups and / or a diamine having 4 to 60 carbon atoms having one or two primary amine groups; b) a lactone and / or carboxylic acid monomer, wherein the lactone or carboxylic acid unit is derived from an acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms, and the lactone and / or carboxylic acid monomer has a repeating unit with a carbonyl from a lactone, hydroxycarboxylic acid, and aliphatic dicarboxylic acid that forms a polyamide oligomer by reacting with a primary or secondary amine nitrogen to form an amide linkage. A thermosetting composition comprising a polyamide repeating unit derived from polymerizing with a lactone and / or carboxylic acid monomer. Claim 3 A thermosetting composition according to paragraph 2, wherein at least 40 mol% of the diamine is a cyclic diamine having a nitrogen atom in a secondary amine group, part of one or more rings, and having 4 to 15 carbon atoms. Claim 4 A thermosetting composition according to claim 2, wherein at least 50 mol% of the diamine is a diamine having two primary amine groups, and the diamine has two primary amine groups of the following structure: Claim 5 A thermosetting composition according to claim 2, wherein the polyamide oligomer is composed of repeating units from a dicarboxylic acid reacted with an amine group, and at least 50 mol% of the dicarboxylic acid component in the amide repeating unit is a dicarboxylic acid having 10 to 50 carbon atoms. Claim 6 A thermosetting composition according to paragraph 2, wherein at least 50 weight percent of the repeating units from a carboxylic acid are derived from a dimeric fatty acid. Claim 7 A thermosetting composition according to claim 2, wherein the combined repeating unit of a diamine and a lactone and / or carboxylic acid monomer forming at least one amide linkage during polymerization into the polyamide is 20 to 60 weight% of the thermosetting composition. Claim 8 A thermosetting composition according to claim 2, wherein the combined repeating unit of a diamine and a lactone and / or carboxylic acid monomer forming at least one amide linkage during polymerization into the polyamide is 25 to 50 weight% of the thermosetting composition. Claim 9 A thermosetting composition according to paragraph 2, wherein at least 90 weight percent of the repeating units from the diamine are derived from a cyclic and / or dicyclic diamine having 4 to 15 carbon atoms, and the nitrogen atoms of the diamine are part of a ring structure. Claim 10 A thermosetting composition according to claim 1, wherein the reactive polyisocyanate or blocked isocyanate is combined where both are present, and is present in the solution in an amount of 10 to 50 weight percent of the solution based on the weight of all components of the composition. Claim 11 A thermosetting composition according to claim 1, wherein the organic diluent is present in an amount of 10 to 50 weight% of the composition. Claim 12 A thermosetting composition according to claim 11, wherein the organic diluent is selected from the group consisting of isopropanol, acetone, dimethyl carbonate, and butyl acetate. Claim 13 A thermosetting composition according to claim 1, wherein the solution is thermosetting after the evaporation of the solvent. Claim 14 A thermosetting composition according to claim 1, wherein the polyisocyanate component has two or more isocyanate groups per polyisocyanate, and the ratio of the isocyanate groups of the polyisocyanate to the combined hydroxyl, amino, and / or carboxyl groups is 2:1 to 1:

1. Claim 15 A thermosetting composition according to claim 1, wherein as the organic diluent evaporates, the polyamide oligomer is crosslinked through a reaction with the polyisocyanate component, which reacts with the hydroxyl, carboxyl and / or amino groups to form covalent chemical bonds, thereby producing a polymer with a number average molecular weight of at least 1,000,000 g / mol. Claim 16 A thermosetting composition formed of a self-supporting film, coating, or adhesive in any one of claims 1 to 15. Claim 17 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 is optionally of the following structure Reacting with a carboxylic acid group, wherein the carboxylic acid unit is from a lactone and / or carboxylic acid component selected from the group consisting of C5 to C8 lactones, C5 to C8 hydroxycarboxylic acids, and aliphatic dicarboxylic acids having 4 to 50 carbon atoms; forming a polyamide oligomer by forming a repeating unit with a carbonyl or nitrogen as part of an amide linkage; and said polyamide oligomer having at least two terminal groups selected from amine, carboxyl, or hydroxyl groups; b) optionally heating said polyamide oligomer to a temperature of 100 to 150°C to make it a more processable liquid; c) adding one or more non-reactive organic diluents; and d) adding to the polyamide oligomer 10 to 40 weight percent of a polyisocyanate component (optional, having blocked isocyanate group(s)), which reacts with 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 with the reaction of an isocyanate, hydroxyl, or amine group with the carboxyl group, - wherein the weight percent of the diamine and carboxylic acid repeating 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 component reactive with the hydroxyl, carboxyl, and / or amino groups is 10 to 40 weight percent of the solution, and at 50% solid content and prior to the reaction of the polyisocyanate, the solution is measured by a Brookfield rotary disc viscometer using a rotation speed of 5 rpm and a #6 spindle, A method comprising having a viscosity of less than 10,000 cps at 25℃. Claim 18 In paragraph 17, the organic diluent evaporates from the solution and the isocyanate group reacts with the hydroxyl, carboxyl, and / or amino group to form a covalent bond, a method. Claim 19 In claim 18, the method wherein at least 50 mol% of the diamine is a cyclic diamine having 4 to 15 carbon atoms, wherein the nitrogen atom is secondary and part of a ring. Claim 20 In claim 18, at least 50 mol% of the diamine is a diamine having two primary amine groups, and the diamine has two primary amine groups of the following structure, method: Claim 21 A method according to any one of claims 17 to 20, wherein at least 50 weight percent of the repeating unit from the carboxylic acid is derived from a dicarboxylic acid having 10 to 50 carbon atoms. Claim 22 In claim 21, the method wherein at least 50 weight percent of the repeating unit from the carboxylic acid is derived from a dimeric fatty acid. Claim 23 A method according to any one of claims 17 to 20, wherein the component reactive to hydroxyl, carboxyl, 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 said blocked polyisocyanate can be added to a polyamide oligomer without concern for chemical reaction until said blocked isocyanate groups are unblocked. Claim 24 A method according to any one of claims 17 to 20, further comprising a process step of adding to the composition one or more compounds having a molecular weight of less than 500 g / mol and having three or more groups reactive with an isocyanate selected from the group of amine, carboxyl, and hydroxyl groups, in an amount of up to 25 weight%, to facilitate crosslinking of the final composition. Claim 25 A method according to claim 17, wherein the polyisocyanate is not added until the composition is ready to form a coating or film, and when the polyisocyanate is added to the polyamide oligomer, the polyisocyanate begins to react with the polyamide oligomer through its isocyanate groups.

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