Matted polyamide-pud

Abstract

To provide polymers.SOLUTION: Polymers are disclosed that incorporate portions of secondary or tertiary polyamide segments connected with polyisocyanates. These polymers have enhanced matting properties. The enhanced matting properties are from creating an inherently matt surface from the polymer without the use of any separate fine particle size matting additives. Conventional matting agents such as fine particle size silica usually result in loss of physical properties such as haze development and porosity in a coating from the matting agent. Composites and hybrids of these polymers and other polyamides, polyurethane and vinyl polymers (acrylates) are also disclosed and claimed.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to waterborne polymers comprising polyamides and multiple urethane and / or multiple urea linked dispersions, which contain polyamide segments derived from cycloaliphatic or aromatic primary or secondary amines reacted with some form of reactive carbonyl, such as carboxylic acid. These polyamides unexpectedly impart a texture, characterized by a lower gloss, to the surface of coatings derived from said polymers comprising polyamides and multiple urethane and / or multiple urea linked dispersions. [Background technology]

[0002] In the coatings industry, sometimes a very smooth coating finish with high gloss is desired. In other cases, a matte (low gloss) coating or ink surface is desired, which reflects incident light in different directions due to variations in the coating surface. Various mechanisms and products have been developed to impart reduced gloss (mattness) for different types of coatings (solvent-based and water-based). The coatings industry seeks uniformity and consistent control of the degree of mattness, as well as the ability to easily adjust the level of mattness, at every stage of the coating manufacturing and coating application process.

[0003] Silica of controlled particle size has been widely used in producing a matte finish. It is believed to work by the silica particles protruding from the coating surface, forming elevated areas on the coating surface that reflect light in various directions. The silica used in this application has a porous structure that increases the porosity of the finished coating (the more silica, the more matte and more porous). The porosity of the coating reduces its resistance to various liquids that can discolor it, mar or soften it, or react adversely with the substrate beneath it (such as causing corrosion of metals). Silica also adds some opacity to the coating because it has a refractive index significantly different from most binders.

[0004] The applicant had two previous applications (US 9,527,961 and US 2016 / 009953) describing polyamide-containing polymer and polyurethane dispersions in which a high proportion of the polyamide is a tertiary polyamide derived from piperazine. Summary of the Invention

[0005] The present invention relates to a polymer comprising polyamide and multiple urethane and / or multiple urea bonds dispersion in an aqueous medium (e.g., water and optionally water-soluble organics), including polyamides from certain cycloaliphatic or aromatic primary or secondary amine groups, which impart a low gloss (high matte) finish to applied coatings derived from the polymer dispersion in an aqueous medium. These polyamides are useful as segments in binders for coatings, inks, or adhesives. These polyamides can also be prepared separately from the primary polymer binder (e.g., a second polymer), both in the form of a dispersion in an aqueous medium. The polyamide and multiple urethane and / or multiple urea bonds polymer can be blended with the second polymer and then the blend can be dispersed in an aqueous medium. Alternatively, the polyamide and multiple urethane and / or multiple urea bonds polymer and the second polymer can each be separately dispersed in an aqueous medium, and then the dispersed particles from each in the aqueous medium can be blended together. Alternatively, these polymers, including polyamides, may be made as masterbatches, optionally with a second polymer, and the masterbatches can be blended with one or more other polymer dispersions to make binders for coatings, inks, or adhesives. The polymers of these resins can be thermoplastic, thermosetting, or elastomeric and are generally aqueous dispersions of these resins. A unique feature of these polymer dispersions with their particular polyamides is their ability to impart a textured surface to the final coating or ink, which gives a reduced gloss (increased matte) coating or ink finish. The amount of polyamide in the coating or ink polymer affects the level of gloss reduction or matte achieved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Definitions: We use parentheses to 1) indicate that something is optionally present, such as monomer(s) meaning one or more monomers, or (meth)acrylate meaning methacrylate or acrylate, 2) to modify or further define the preceding term, or 3) to recite a narrower embodiment.

[0007] The term "hydrocarbyl" or "hydrocarbylene" refers within the context of the present invention to a group having a carbon atom directly attached to the remainder of the molecule and having a hydrocarbon or predominantly hydrocarbon character. Such groups include purely hydrocarbon groups, i.e., aliphatic, and, where appropriate, non-hydrocarbon substituents (including heteroatoms) that do not alter the predominantly hydrocarbon character of the group. Examples of non-hydrocarbon substituents include hydroxy, nitro, cyano (wherein the cyano group is attached via a C atom, as is acyl), alkoxy, acyl groups, etc. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen, and sulfur.

[0008] The first part of the invention is the production of polyamide segments from cyclic aliphatic or aromatic primary or secondary diamine type components reacted with some form of reactive carbonyl such as a carboxylic acid (often a dicarboxylic acid, a hydroxycarboxylic acid or a lactone from a hydroxycarboxylic acid). In a preferred embodiment, both nitrogen atoms are attached to a cyclic or aromatic ring with no intervening atoms between the nitrogen and the ring. This reaction of the amine with the carboxylic acid produces water (or a hydroxyl group in the case of a lactone) and an amide bond as a by-product. The formation of the polyamide segments can be facilitated by removing the water by-product. Generally, polyamide number average molecular weights of about 500-5,000 g / mol, more preferably about 800 or 1000-3000 g / mol, are readily processable by this technique into final binders. Applicant uses polyamide in the sense of two or more amide bonds in an oligomer or polymer. These polyamides may be initially amine, hydroxyl, or carboxylic acid terminated. Generally, it is desirable to form hydroxyl end groups since these are the conventional end groups for precursors to polyurethanes.

[0009] Many of the examples use a slight excess of diamine relative to the moles of reactive carbonyl and / or carboxyl functional groups, which upon reaction results in a very low acid number and consumes virtually all of the available carboxyl groups. Adjusting the stoichiometry of the reactive amine and acid groups helps control the molecular weight and the predominant end group. In some embodiments, the only carboxylic acid groups are hydroxycarboxylic acids or their lactones, resulting in a hydroxyl-terminated polyamide that forms a polyurethane when reacted with a polyisocyanate.

[0010] In other embodiments, the amine repeat units are first reacted with a dicarboxylic acid to make an amine-terminated polyamide, and then the polyamide is chain extended at the ends of the amine-terminated polyamide by lactone polymerization. Other reactants (e.g., trifunctional amines or trifunctional carboxylic acids or monofunctional amines or monofunctional carboxylic acids) or impurities can be included in the polyamide formation as long as they are used in small amounts relative to the required reactants and do not unduly increase or decrease the molecular weight of the reaction product.

[0011] Preferred cycloaliphatic or aromatic and primary or secondary diamine reactants are represented by formulae Ib to IVb below: [ka] Or a combination thereof.

[0012] wherein R1-R5 are independently selected from H or a C1-C4 straight or branched chain alkyl group, and in one embodiment, desirably at least 80, 90 or 95% by weight of all R5 groups of the amine repeat units are H.

[0013] Preferred cycloaliphatic or aromatic and primary or secondary diamine repeat units are of formulae I-IV: [ka] Or a combination thereof.

[0014] wherein R1-R5 are independently selected from H or a C1-C4 straight or branched chain alkyl group, and in one embodiment, desirably at least 80, 90 or 95% by weight of all R5 groups in the amine repeat units are H, and at least 80, 90 or 95% by weight of the cycloaliphatic or aromatic portion of the molecule are cycloaliphatic, such that Formula 1 and Formula II (preferred) are Ia and IIa as shown below: [ka]

[0015] where R4-R1 are independently H or a C1-C4 alkyl group. In one embodiment, the amine repeat units of the polyamide or polyamides are prepared by At least 60, 70 or 80 of the R1, R2, R3 and R4 groups of the diamines of Formulae Ib-IVb, I-IV and Ia-IIa are hydrogen. In one embodiment, desirably at least 80, 90, 95, 99 or 100 mole percent of the R5 groups are hydrogen, and these primary amines to give primary diamines react to give polyamides. [ka] and [ka] To generate a repeat unit of where R1-R4 are as above. Examples of aliphatic primary cyclic diamines include 1,3-diaminocyclohexyl, and 4,4'-methylenebis(cyclohexylamine), optionally mono- or di-alkyl (methyl is preferred) substituted as taught above. Although cyclic aliphatic and cyclic aromatic diamines are shown, it is believed that aromatic diamines may produce a yellow color in polymer coatings and inks when exposed to a light source. Thus, primary aliphatic and / or secondary diamines are slightly preferred.

[0016] The amount of primary and / or secondary diamines having specific aliphatic cyclic structures or aromatic structures of formulas I-IV having amine groups bonded directly to carbon atoms in the cyclic structures incorporated as the amine compound backbone is from about 1 or 2 to about 20 or 25 weight percent of the total polymer in the polymer dispersion, more desirably 4 to 15, preferably 6 to 15 based on the total amount of polymer in the polyurethane dispersion (i.e., generally the coating weight is less than the weight of the aqueous phase, fillers, and pigments).

[0017] In one embodiment, the diacid reacted with the aliphatic cyclic diamine component is 10 ~C 40 C4-C including dicarboxylic acids and dimer fatty acids 50または60 Dicarboxylic acids. Particularly preferred larger diacids include sebacic acid, dodecanoic acid, and dimer acid. Repeating units derived therefrom have the structure [ka] In the formula, Ra is C2 to C 48または58 , more preferably C8 to C 38 Hydroca Preferred diacids are sebacic acid and C 10 ~C 40 Dimer and trimer fatty acids are very useful in this application.

[0018] The terms dimer fatty acid (also called dimer diacid or dimer fatty diacid) and trimer fatty acid are well known in the art and refer to the dimerization or trimerization products of mono- or polyunsaturated fatty acids and / or their esters. They are prepared by polymerizing fatty acids under pressure and then removing most of the unreacted fatty acid starting material by distillation. The final product usually contains small amounts of mono- and trimer fatty acids, but is mostly composed of dimer fatty acids.

[0019] The dimer and trimer fatty acids used in the present invention are preferably 10 ~C 30 Fatty acids, more preferably C 12 ~C 24 Fatty acids, specifically C 14 ~C 22 Fatty acids, more preferably C 16 ~C 20 Fatty acids, especially C 18It is derived from the dimerization product of fatty acids. The resulting dimeric fatty acid thus preferably contains carbon atoms per molecule in the range of 20 to 60, more preferably 24 to 48, particularly 28 to 44, even more preferably 32 to 42, and especially 36. Preferably, the fatty acid starting material used to make the dimer is a straight chain monounsaturated fatty acid.

[0020] The molecular weight (weight average) of the dimeric fatty acids is preferably in the range of 450 to 690, more preferably 500 to 640, in particular 530 to 610, especially 550 to 590 g / mol. The molecular weight (weight average) of the trimer fatty acids is preferably in the range of 750 to 950, more preferably 790 to 910, in particular 810 to 890, especially 830 to 870. In addition to the dimeric fatty acids, dimerization usually results in the residues of trimer fatty acids (so-called "trimers"), oligomeric fatty acids, and monomeric fatty acids (so-called "monomers") in various amounts, or esters thereof, present. They are available from Croda under the trademark Pripol™ or from Arizona Chemical under the trademark Unidyme™.

[0021] The dimer fatty acid used in the present invention may preferably have a dimer fatty acid (or dimer) content of more than 60% by weight, more preferably more than 70% by weight, particularly more than 80% by weight, especially more than 85% by weight. In addition, particularly preferred dimer fatty acids may have a trimer fatty acid (or trimer) content of less than 40% by weight, more preferably less than 30% by weight, particularly less than 20% by weight, especially less than 15% by weight. Furthermore, the dimer and / or trimer fatty acid preferably contains less than 10% by weight, more preferably less than 6% by weight, particularly less than 4% by weight, especially less than 3.5% by weight of mono fatty acid (or monomer). All the above weight percentage values ​​are based on the total weight of the polymerized fatty acid and mono fatty acid present.

[0022] Formula HO-C(=O)-R F Preferred hydroxycarboxylic acids having -OH and the formula derived therefrom [ka] The cyclic lactone is R f has 1 to 14 carbon atoms, more preferably 1 to 4 carbon atoms) f The various unsubstituted and alkyl-substituted caprolactones and valerolactones are preferred. When starting from a hydroxycarboxylic acid, both the hydroxycarboxylic acid and the lactone derived therefrom are formed with the formation of one mole of water. Structure-(C(=O)-R f -O-)- repeating units.

[0023] As noted in the Summary of the Invention, hydroxycarboxylic acids or lactones therefrom can be used with or without dicarboxylic acids (or vice versa) to form amide linkages, and the lactones or hydroxycarboxylic acids can be used to chain extend the polyamides of the invention with polyester repeat units. When the polyamides are chain extended with polyester repeat units from hydroxycarboxylic acids or lactones derived therefrom, the amount of polyester repeat units desirably ranges from about 1 to about 75 weight percent of the polymer in the polyurethane dispersion.

[0024] A polyamide repeat structure of one mole of a diacid and one mole of a particular primary diamine looks like this: [ka] The primary diamine component looks like this: [ka] Diamine R b appears as a structure selected from the group [ka] where R1-R4 are as above. If the amine repeat unit was a secondary amine type with an R5 group other than hydrogen, the structure would have the R5 group on the nitrogen of the amide bond. These repeat units are most common in polyamides, but monofunctional or trifunctional amide-forming reactants may be present, so long as at least 50, 70, 80, 90 or 95 mole percent of the amine reactants are difunctional.

[0025] A second embodiment of the present invention is to a) incorporate or blend a second, third or more polymer(s) into a polyamide and a polymer comprising multiple urethane and / or multiple urea linkages dispersed in an aqueous medium, or b) make separate dispersions of a polyamide and a polymer comprising multiple urethane and / or multiple urea linkages and a second, third or more polymer(s) in an aqueous medium that are then blended as dispersions to form a blend. These two procedures are desirable because the amount of the polyamide having repeat units and the polymer containing multiple urethane and / or multiple urea linkages controls the relative amount of matte or gloss reduction in the final film of the polymer. The level of matte or gloss reduction can be controlled by blending two polymers, a polymer containing a polyamide having repeat units of formulas I-IV and a polymer(s) substantially lacking repeat units of formulas I-IV. A combination of a) and b) can be used, where one second polymer is blended with the polyamide and the polymer containing multiple urethane and / or multiple urea linkages before dispersing in the aqueous medium, and the third polymer is made into a separate dispersion in the aqueous medium and then blended with the polyamide and the polymer containing multiple urethane and / or multiple urea linkages and the second polymer that was blended before dispersing in the aqueous medium. Applicants generally use the term incorporated to mean covalently bonded to the polyurethane when discussing the polymer segments of the polyurethane. Applicants generally use the term blended to mean forming a physical blend.

[0026] Variations of the above embodiments of the invention (used in combination as appropriate) include the option of incorporating polyamides and polymers containing multiple urethane and / or multiple urea linkages into larger polyurethane structures by polymerizing a) ester-forming monomer(s) and / or b) other polyamide-forming monomer(s) onto the polyamide chain ends, or by linking the polyamide to other larger oligomeric or polymeric species, for example, by reaction of Zerewitinoff reactive groups on the oligomeric or polymeric species with polyisocyanates.

[0027] In one embodiment, polyester segments are added to one or both ends of the polyamide polymer by ester polymerization. This can be accomplished by adding polyester-forming monomer(s) to the polyamide, optionally catalyzing the ester polymerization, and stirring and heating the reactants. In one embodiment, poly(caprolactone) can be added to one or both ends of the polyamide by ester polymerization. The molecular weight of the polyester segments can be controlled by the amount of polyester-forming reactants added relative to the number of polyamide segments and the reaction conditions. Alternatively, dicarboxylic acids and dihydroxyl compounds can be polymerized in the presence of the polyamide and partially or completely bonded to the polyamide by conventional condensation polymerization.

[0028] Alternatively, the polyamides from cycloaliphatic or aromatic and primary or secondary polyamines can be bonded to other monomers, or oligomeric or polymeric species, by polymerizing different polymeric structures directly from the monomer(s) to or with the polyamides. For example, polyester, polyether, or polycarbonate segments with about two terminal Zerewitinoff groups per segment can be bonded with polyisocyanates on polyamide segments that provide matte. Polyether, polyester, polycarbonate segments with about two Zerewitinoff groups per segment are desirable because it is believed that linear polymers result when the polyisocyanate has about two reactive isocyanate groups per polyisocyanate. Small amounts of monofunctional or trifunctional reactants can be used with known similar results (especially when the amounts of monofunctional and trifunctional reactants are about equal in moles, the average functionality remains about 2). However, if too much mono- or trifunctional reactant is used, the molecular weight of the product may be too low or too high. Zerewitinoff groups are well known and are defined as active hydrogen-containing groups (such as amines or hydroxyls, which are the primary Zerewitinoff groups of this disclosure) that react with isocyanates to form covalent chemical bonds called urea or urethane bonds. When a urethane bond is formed, the bond is formed between a hydroxyl group and an isocyanate. When the bond is between an amine group and an isocyanate group, a urea bond is formed. In a preferred embodiment, the polyester, polyether, or polycarbonate segment having Zerewitinoff end groups has a number average molecular weight of about 500 to about 5,000 g / mol.

[0029] The number average molecular weight can be calculated when the polyester, polyether, or polycarbonate is difunctional, simply dividing the number of grams of the segment in the sample by (0.5 times the number of functional groups in moles in the sample) gives the number and type of functional groups per polymer segment. The number average molecular weight can also be determined by gel permeation chromatography (GPC) in a good solvent such as tetrahydrofuran, calibrating the GPC column with a series of commercially available polystyrene calibration samples of known molecular weight. In general, the two methods give very similar molecular weights.

[0030] A series of polyamide oligomers were made from conventional difunctional acids and alicyclic primary diamines. The initial oligomers may contain amine end groups, carboxyl end groups, or other end groups derived by reacting the terminal amine or carboxyl groups with other reactants. The presence of strong hydrogen bonds in these structures makes them less likely to deform during film formation, which is believed to promote the formation of the desired textured coating surface with a high matte / low gloss finish when the film is formed from the aqueous dispersion, although not wishing to be bound by theory. This also occurs at low molecular weights in the case of polyamides from certain aliphatic or aromatic cyclic primary or secondary diamines.

[0031] Many of the oligomers, telechelics, and polymers herein are made by condensation reactions of reactive groups on the desired mono- or dicarboxylic acid monomers and alicyclic and / or aromatic primary or secondary diamine monomer(s). Triamine monomers and tricarboxylic acids are less desirable for this because they are believed to produce highly branched, less deformable polyamides. These condensation reactions of carboxylic acid groups with amine or hydroxyl groups are well known and are facilitated by the removal of water and / or catalysis. The reaction of carboxylic acid groups with amine groups to form amides can be catalyzed by boric acid, borate esters, boranes, phosphorous acids, phosphates, phosphate esters, amines, acids, bases, silicates, and silsesquioxanes. Additional catalysts, conditions, etc. are available in textbooks such as "Comprehensive Organic Transformations" by Larock.

[0032] Two previous applications (US9,527,961 and US2016 / 0009953) described tertiary polyamide containing polymers and polyurethane dispersions in which a high percentage of the amide bonds are tertiary amide bonds derived from piperazine and other secondary diamines. These polymers were not themselves matte or low gloss in coating applications. In one embodiment of the present disclosure, it is desirable to blend (before or after dispersing in an aqueous medium) or incorporate the polyamides of the present disclosure and matte polymers containing multiple urethane bonds and / or multiple urea bonds with previous tertiary polyamide-containing polymers. This provides various levels of flattening or gloss reduction to these polyamides. In one embodiment, it is desirable to include from 5 to 85 weight percent, more desirably at least 10, 15, 20 or 25 weight percent and up to about 65 weight percent polyamide (based on the total weight of the polymer(s) in the polyamide-containing polyurethane dispersion in aqueous medium), where the polyamide is characterized as having at least 75 weight percent amide repeat units, at least 60, 75 or 80 mole percent of the amide linkages are tertiary amide linkages, and at least 60, 70 or 80 weight percent of the amine groups in the amide repeat units are cyclic diamines, in which the nitrogen atom is part of a ring and has from 3 or 4 to 10 carbon atoms, such as piperazine or mono- or di-alkyl (C1-C4) substituted piperazines.

[0033] The tertiary polyamides of those earlier disclosures had a lower minimum film formation temperature (generally about -10 to about 20, 25 or 30°C) than most polyamides from primary amines so that they could form films at or near room temperature (about 20-25°C) without the use of significant amounts of plasticizers, solvents or coalescing aids. The tertiary amide linkages of those disclosures were formed from covalent bonds between secondary amines and carboxylic acid groups resulting in tertiary amide linkages (an important aspect of those earlier disclosures is the attainment of lower minimum film formation temperatures). Primary amines react with carboxylic acid type groups to form secondary amides, which generally have a higher minimum film formation temperature, other factors being kept the same.

[0034] For example, N-methylaminoethanol or HN(R α )(R β It may be desirable to convert the carboxylic acid terminated polyamide segments to hydroxyls (Zerewitinoff groups) by reaction with an amino alcohol such as, for example, R α is a C1-C4 alkyl group, and R β is an alcohol group and C2-C 12 Contains an alkylene group or alternatively R α and R β are interconnected to form a ring structure and a C3-C cyclic structure containing a pendant hydroxyl group (as in 2-hydroxymethylpiperidine). 16 Alkylene groups may be formed, any of which can form polyamides with terminal hydroxyl groups. The reaction of secondary amines (as opposed to hydroxyl groups) with carboxylic acids may be favored 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.

[0035] In one embodiment, the polymers containing polyamide and multiple urethane and / or multiple urea linked dispersions are copolymerized or blended with other polyamide-containing polymer dispersions (described as initial tertiary polyamides) as described in the next few paragraphs. Preferred dicarboxylic acids for forming the initial tertiary polyamides are those where the alkylene portion of the dicarboxylic acid is a cyclic, straight, or branched chain (optionally containing aromatic groups) alkylene of 2 to 36 carbon atoms, more preferably 4, 8 or 12 to 36 carbon atoms, optionally containing up to one heteroatom per 3 or 10 carbon atoms (the diacid contains 2 more carbon atoms than the alkylene portion). These include dimer fatty acids, hydrogenated dimer acids, sebacic acid, and the like. In general, applicants prefer diacids with larger alkylene groups, since they generally provide polyamide repeat units at lower film formation temperatures.

[0036] Preferred diamines for forming the tertiary polyamides include those having 6 to 60 carbon atoms, more desirably 6 to 20, preferably 6 or 12, or 13 to 15, 17 or 20 carbon atoms, optionally containing one heteroatom (excluding the two nitrogen atoms) for every 3 or 10 carbon atoms of the diamine, and optionally containing a variety of cyclic, aromatic, or heterocyclic groups, provided that one or both of the amine groups are primary 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(s)) alkylene group of 2 to 36 carbon atoms, more preferably 2 or 4 to 12 carbon atoms (optionally containing up to 1 or 3 heteroatoms per 10 carbon atoms of the diamine); R c and R d are individually , a straight or branched chain alkylene group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms, or optionally R c and R d may be joined together to form a single straight or branched chain alkylene group of 1 to 8 carbon atoms, or, as appropriate, R c and R d One of the carbon atoms is R b and more preferably R c and R d are bonded together to combine 1 or 2 to 4 carbon atoms.

[0037] In one embodiment of the prior disclosure regarding tertiary polyamides, desirably at least 50% by weight, more desirably at least 60, 70, 80 or 90% by weight of the polyamide oligomer or telechelic polyamide comprises repeat units from a diacid, the structure of which is: [ka] In the formula, R a is the alkylene portion of the dicarboxylic acid and is a cyclic, straight or branched chain (optionally containing aromatic groups) alkylene of 2 to 36 carbon atoms, more preferably 4 to 36 carbon atoms, optionally containing up to one heteroatom per 3 or 10 carbon atoms of the diacid (the diacid form contains 2 more carbon atoms than the alkylene portion of the diacid); In the formula, R b is according to the following formula: [ka] In the formula, R b is 2 to 36 or 60 carbon atoms, more preferably 2 or 4 to 12 carbon atoms; R c and R d are individually straight or branched chain alkyl groups of 1 to 8 carbon atoms, more preferably 1 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 are bonded together to form an alkylene group of 1 or 2 to 4 carbon atoms.

[0038] During the reaction of the polyamides of the present disclosure with polyisocyanates to form polyamide-containing polyurethanes, other species can be present along with the Zerewitinoff groups to co-react with the resulting polyurethane. These can be low molecular weight species (e.g., diols or diamines less than 500 g / mole) or high molecular weight species (e.g., 500-5,000 g / mole oligomers added to form high or low Tg phases in the resulting urethane polymer). In general, when a low viscosity prepolymer is desired to make a polymer dispersion in an aqueous medium, one only reacts components that have a stoichiometric imbalance between reactive groups to form a medium molecular weight species, referred to as a prepolymer, with the functional groups present in excess that are the primary termini of the majority of the prepolymer units. This is usually accomplished by keeping the stoichiometric ratio of isocyanate groups to Zerewitinoff groups away from a 1:1 ratio (a prepolymer with limited molecular weight is produced due to an excess of isocyanate or Zerewitinoff groups acting as end groups). The molecular weight of the prepolymer is The viscosity of the prepolymer is fairly low (5,000 g / mole to 100,000 g / mole), so that the prepolymer is liquid at or slightly above room temperature (typically up to about 80°C). This low viscosity below 80°C facilitates mixing and shearing of the liquid prepolymer to form a stable finely dispersed colloidal prepolymer phase in water. Often an excess of isocyanate groups is used so that the prepolymer is isocyanate terminated.

[0039] The molecular weight of the urethane prepolymer can be increased after dispersion of the prepolymer has been performed (or it is sometimes referred to as chain extending the prepolymer into the urethane polymer). This can be done by adding to the dispersion low molecular weight species such as diols, triols, tetrols, or diamines, triamines or tetraamines that can react with the isocyanate terminated prepolymers to link them to higher molecular weight species. The isocyanate groups of the prepolymer can also react with the water of the continuous phase to produce CO2 gas and terminal amine groups on some of the prepolymers. The amine groups of some of the prepolymers can then react with the isocyanate groups of other prepolymers to chain extend both species. The next paragraph describes dispersing groups that can be incorporated into the prepolymer / polymer, but it is also possible to utilize anionic, cationic, nonionic, or zwitterionic dispersants and surfactants or mixtures thereof to facilitate dispersion of the prepolymer / polymer in the continuous medium.

[0040] When it is desired to disperse a prepolymer (or polymer) in a continuous aqueous phase, it is desirable to add surface active dispersing species to the prepolymer (or polymer), such as anionic, cationic, nonionic, or zwitterionic species. These dispersing species serve to provide colloidal stabilization to the dispersed phase. When surface active dispersing groups are incorporated into the polymer, it is desirable to include them in the reaction of the polyamide oligomer (e.g., during the preparation of a urethane prepolymer) or other source of Zerewitinoff reactive groups. Dispersing groups having Zerewitinoff reactive groups that react with isocyanate groups to form urea or urethane linkages are particularly preferred for this purpose.

[0041] When it is desired to form a polyurethane dispersion in an aqueous medium, it is desirable to include a water-dispersing component, either as a surfactant / emulsifier or as a water-dispersing group that can be incorporated into the polyurethane itself. Thus, it is often desirable to include at least one water-dispersibility enhancing compound, i.e., a dispersing functional monomer having at least one hydrophilic, ionic or potentially ionic group, in the reactants for the urethane-forming polymers and prepolymers of the present invention to aid in the dispersion of the polymer / prepolymer in the aqueous medium. Typically, this is done by incorporating into the polymer / prepolymer chain (through one or two Zerewitinoff groups of the compound) a compound that carries at least one hydrophilic group or a group that can be made hydrophilic by chemical modification, e.g., neutralization. These compounds can be nonionic, anionic, cationic, zwitterionic, or a combination thereof. For example, anionic groups, such as carboxylic acid groups, can be incorporated into the prepolymer and subsequently ionized by a salt-forming compound, such as ammonium hydroxide or a tertiary amine, as defined in more detail below. Anionic dispersible urethane prepolymers / polyurethanes based on carboxylic acid groups generally have an acid number of from about 1 to about 60 mg KOH / gram, typically from 1 to about 40, or even from 10 to 35 or from 12 to 30 or from 14 to 25 mg KOH / gram. Other water-dispersibility enhancing compounds can also be reacted into the urethane prepolymer backbone through urethane or urea linkages containing lateral or terminal hydrophilic ethylene oxide or ureido units.

[0042] Particularly interesting water-dispersibility enhancing compounds are those which can incorporate weak carboxyl groups into the prepolymer. Typically, they have the general formula (HO) × Q(COOH) y where Q is a linear or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are 1-3). Examples of such hydroxycarboxylic acids include dimethylolpropanoic acid, dimethylolbutanoic acid, citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixtures thereof. Dihydroxycarboxylic acids are more preferred, with dimethylolpropanoic acid and dimethylolbutanoic acid being most preferred.

[0043] Another group of water-dispersibility enhancing compounds of particular interest are side-chain hydrophilic monomers. Some examples include alkylene oxide polymers and copolymers in which the alkylene oxide group has 2-10 carbon atoms, as shown, for example, in U.S. Pat. No. 6,897,281, the disclosure of which is incorporated herein by reference. There are commercially available polyethers with two terminal hydroxyl groups near one end of the polyether that can be incorporated into urethanes and urethane prepolymers as non-ionic dispersing moieties. They have a significant portion of the polyether extending from these two attachment points at one end of the polyether in a urethane-tethered manner. These include Tegomer® D3403 used in U.S. Pat. No. 6,897,381 and Perstop's Ymer®.

[0044] The water-dispersibility enhancing compound can impart cationic properties to the polyurethane. Cationic polyurethanes contain cationic centers incorporated or attached to the backbone. Such cationic centers include ammonium, phosphonium and sulfonium groups. These groups can be polymerized to the backbone in ionic form or can be generated by post-neutralization or post-quaternization of the corresponding nitrogen, phosphorus or sulfur moieties, as required. All combinations of the above groups, as well as combinations with non-ionic stabilization, can be used. Examples of amines include N-methyldiethanolamine and amino alcohols available from Huntsman under the Jeffcat® tradenames, such as DPA, ZF-10, Z-110, ZR-50, etc. They can form salts with virtually any acid. Examples of acids include hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid, perchloric acid, citric acid, tartaric acid, chloroacetic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-carboxyethyl acrylate and others. Quaternizing agents include methyl chloride, ethyl chloride, alkyl halides, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, dimethyl sulfate, diethyl sulfate, chloroacetic acid, etc. Examples of quaternizing diols include dimethyldiethanolammonium chloride and N,N-dimethyl-bis(hydroxyethyl) quaternary ammonium methanesulfonate.

[0045] Other suitable water-dispersibility enhancing compounds include thioglycolic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol, and the like, and mixtures thereof.

[0046] Although the use of water-dispersibility enhancing compounds is preferred, the dispersions of the invention can be prepared without them by using high shear dispersion techniques and stabilizing with surfactants.

[0047] Polyisocyanates Suitable polyisocyanates have an average of about 2 or more isocyanate groups per molecule, preferably an average of about 2 to about 4 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. Polyisocyanates are represented by the formula: [ka] (In the formula, R Q is a hydrocarbylene group of 5 to 20 carbon atoms, optionally containing one or more cycloaliphatic structures or one or more aromatic rings, and Z is 1 to 4, more desirably 1 to 3, and preferably on average predominantly 2).

[0048] 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, 2-methyl-1,5-pentamethylene diisocyanate, and the like. 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.

[0049] 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.

[0050] 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.

[0051] Examples of suitable aromatic polyisocyanates include 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate, their isomers, naphthalene diisocyanate, etc. Preferred aromatic polyisocyanates include 4,4'-diphenylmethylene diisocyanate and toluene diisocyanate.

[0052] Examples of suitable heterocyclic isocyanates include 5,5'-methylenebisfurfuryl isocyanate and 5,5'-isopropylidenebisfurfuryl isocyanate.

[0053] Conventional Blends with Other Polymers The polyamide and polymer containing multiple urethane and / or multiple urea bonds formed in the dispersion of the present invention can be combined with a compatible polymer (i.e., a second polymer) and / or polymer dispersion by methods well known to those skilled in the art. In general, the second polymer can be distinguished from the polyamide and polymer containing multiple urethane and / or multiple urea bonds of the dispersion because it is not covalently bonded to the polyamide and polymer containing multiple urethane and / or multiple urea bonds and / or has less than the specified amount of amine repeat units of formula I and / or II that define the unique polymer of the present disclosure. Such polymers, polymer solutions, and dispersions can be prepared by the methods described in AS Teat. "Resins, Water-Soluble" in: Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons. 3rd Edn., Vol. 20, HF Mark et al. Eds., pp. 207-230 (1982).

[0054] Composite polymer compositions (e.g., free radical polymerizable Monomer-containing polyurea / urethane In one embodiment, ethylenically unsaturated monomer(s) can be used as a solvent to reduce the viscosity of the prepolymer during preparation and dispersion of the polyamide and multiple urethane and / or multiple urea linkage-containing prepolymer or polymer, and subsequently polymerize the unsaturated monomer(s) to form the polymer. Ethylenically unsaturated monomers and other free radical polymerizable monomers can be polymerized by conventional free radical sources to form polymers within the polyamide and multiple urethane and / or multiple urea linkage-containing polymer particles, and to form composite polymers with the polyamide and multiple urethane and / or multiple urea linkage-containing polymers of the dispersion. Vinyl polymers are a general term for polymers derived from or derived from a substantial portion of unsaturated monomers. Acrylic is often considered a subset of vinyl and refers to acrylic acid, acrylates, which are esters of acrylic acid, and alkacrylates, such as methacrylates and ethacrylates, and polymers therefrom. Various styrene and alkyl-substituted styrene type monomers, such as divinylbenzene, (meth)acrylonitrile, vinyl esters such as vinyl acetate, unsaturated amides such as acrylamide, dienes of 4-6 carbon atoms, vinyl monomers with dispersing moieties such as AMP monomer (2-acrylamido-2-methylpropanesulfonic acid), and other vinyl monomers readily copolymerize with acrylic monomers. Additional free-radically polymerizable materials, such as other unsaturated monomers, may be added to and copolymerized with the vinyl or acrylic monomers. These other monomers may be monomers that are not strictly ethylenically unsaturated, such as maleic anhydride, maleic acid, and other monomers whose carbon-carbon double bonds are about as reactive (and copolymerizable) as ethylenically unsaturated monomers. Dienes are considered ethylenically unsaturated and will copolymerize with both the broad category of vinyl monomers and the narrow category of acrylic monomers.

[0055] Polymerization within polyurethane particles can be carried out by forming an aqueous dispersion of the polymer containing polyamide and multiple urethane and / or urea bond complexes, and then polymerizing additional monomers in the presence of those dispersions by emulsion or suspension polymerization. Another way to make composite polymers is to include ethylenically unsaturated monomers in the prepolymer form of polyamide and multiple urethane and / or urea bond polymers, for example, with the reactants to form the prepolymer and / or before dispersing the polyurethane prepolymer, and polymerize these monomers before, during, and / or after dispersing the prepolymer in an aqueous medium. The weight percent of the polymer(s) from the free radically polymerizable monomer (or polymer therefrom) based on 100 parts of the combined polyamide and multiple urethane and / or multiple urea bond polymer, free radically polymerizable monomer, and any additional blended or incorporated polymer is at least 1, 5, or 10 weight percent, desirably up to 30, 40, or 50 weight percent of the combined polymer in the polymer containing polyamide and multiple urethane and / or multiple urea bond dispersion.

[0056] In one approach, free radically polymerizable monomers (ethylenically unsaturated monomers) act as diluents (or plasticizers) during prepolymer formation, with and without free radically polymerizable monomers (e.g., acrylics) or polymers thereof; composites of the polyamides and polymers containing multiple urethane and / or multiple urea linkages of the present invention can be made by any of these approaches.

[0057] Expanding the definition of complex and / or hybrid polymers dispersed in aqueous media Composites (also known as hybrid compositions) are made by combining polyamides and other repeating units in the polymer containing multiple urethane and / or urea linkages (e.g., polyethers, polycarbonates, polyethers ... This technique allows one to adjust the weight percent of polyamide repeat units relative to the polyester segments, polysiloxanes, etc. Thus, this technique provides several ways to independently control the amount of polyamide in the composite polyurethane particles, which can affect the polarity or hydrogen bonding of the composite particles, the surface tension of the composite particles, and / or the modulus, tensile strength, etc. of the composite polymer at certain critical temperatures.

[0058] By the term composite and / or hybrid, we intend to include various mixtures of polyamide-rich polymer types, such as polyamides and polymers containing multiple urethane and / or multiple urea linkages, with other polymers. Polymers containing polyamide segments may have other comonomers or comonomer segments linked directly or indirectly to the polyamide segments. These comonomers may include polyethers, polyesters, polycarbonates, polysiloxanes, and the like. The composite and / or hybrid polymers of the composite and / or hybrid dispersions have about the same particle size ranges as those disclosed for the polyurethane dispersions in water.

[0059] The composite and / or hybrid polymer dispersions may have anionic, nonionic, or zwitterionic colloidal stabilizing groups within the polymer, as previously disclosed.

[0060] Water may be present in an amount of about 10, 20, or 30 weight percent to about 70, 80, or 90 weight percent of the polyamide and polymer containing multiple urethane and / or urea linkages in the form of a dispersion in an aqueous medium. Typically, lowering the water content can save on shipping costs for the same amount of polymer, but minimizing the water content tends to increase the viscosity of the dispersion.

[0061] In one embodiment, it is desirable to partially crosslink the polyamide and the polymer containing multiple urethane and / or multiple urea linkages, or one of the second or third polymers therein, to enhance the physical properties of the polymer, such as tensile strength and modulus. This can be accomplished by adding various crosslinking functional groups to the polymer in the dispersion, or by adding another crosslinking component to the polyamide and the polymer containing multiple urethane and / or multiple urea linkages in the form of a dispersion. The crosslinking component can include polyisocyanates, blocked polyisocyanates, aziridines, ketone-hydrazine crosslinks, and the like. Polyisocyanates, blocked polyisocyanates, and ketone-hydrazine crosslinks are each preferred types.

[0062] Reactive crosslinking moieties of the blocked isocyanate (e.g., MEKO) or 1,3-dicarbonyl compound type (e.g., DEM) allow for the delivery of two-component performance with a one-component system. Several types of compounds can be used as blocking (aka protecting or masking) agents to provide crosslinking functionality in urethane polymers and coating compositions. Their function is to temporarily protect the isocyanate groups from undesired reactions. The main requirement for blocking compounds is that their reaction with isocyanates is reversible. When the reaction is reversed, the isocyanate groups are regenerated and available for further reaction after deblocking. The deblocking reaction can be induced by physical or chemical means, e.g., high temperature, radiation, vacuum, catalysts, compounds containing active hydrogen, or combinations thereof. Malonates (e.g., DEM) are a variant of blocking compounds because they block isocyanate groups from undesired reactions with water, etc., but when combined with hydroxyl-containing substrates, they react at low temperatures to form chemical bonds with such reactive hydroxyls rather than deblocking at high temperatures during crosslinking.

[0063] Examples of reactive crosslinking moieties (including blocking agents) include 1,3-dicarbonyl compounds, oximes and other N-hydroxyl compounds, phenols, alcohols, lactams, imines, and the like. Examples of reactive crosslinking agents include dazoles, pyrazoles, acids, mercaptans, imides, secondary amines, cyanoacetates, malononitrile and its derivatives, and sulfites. Preferred reactive crosslinking agents (including blocking agents) are 1,3-dicarbonyl compounds (dicarbonylmethanes) (US 2,826,526). Examples include acetylacetone and its derivatives, alkylacetoacetates, alkoxyalkylacetoacetates, barbituric acid and its derivatives. The reactive crosslinking moiety can be reacted to a prepolymer and then to a polyurethane, or the reactive crosslinking moiety can be another isocyanate-based compound / moiety (e.g., a blocked polyisocyanate moiety or the reaction product of a polyisocyanate with a 1,3-dicarbonyl compound) that reacts to crosslink or bond the polyurethane to a substrate.

[0064] Oximes are another group of currently preferred blocking agents. Oximes can be represented by the general formula CRR'=NOH, where R and R' are independently H or C. n H 2n+1 R and R' may also include groups with heteroatoms, including alicyclic, aromatic, and heterocyclic groups. The oxime may be an aldoxime when one or both of R and R' are hydrogen, or a ketoxime when both R and R' are hydrocarbyl groups, preferably alkyl groups having 1 to 12 carbon atoms. Examples of aldoximes include formaldoxime, acetaldoxime, propionaldoxime, butylaldoxime, benzaldoxime, and the like. Examples of ketoximes include acetoxime, butanone oxime, methyl ethyl ketoxime (MEKO), methyl isobutyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, acetophenone oxime, and the like. The 1,3-dicarbonyl compounds and oximes may be used alone or in combination. They may be partially replaced with other blocking agents.

[0065] Other blocking agents include lactams, secondary and tertiary alcohols, phenols, pyrazoles, mercaptans, N-hydroxyl compounds, and mixtures thereof. Some specific examples of other suitable blocking agents include triazoles, tetrazoles, imidazoles, caprolactams, phenols, and derivatives thereof, such as esters of hydroxybenzoic acid, pyrazoles, 3,5-dimethylpyrazoles, dibutylamines, diisopropylamines, piperidines, piperazines, tert-butanol, cyclohexanol, isopropanol, glyceryl carbonate, N-hydroxysuccinimide, hydroxypyridines, and esters of hydroxamic acid. When stepwise reactions are desired, combinations of two or more blocking agents are preferred, especially mixtures of blocking agents that unblock at different temperatures.

[0066] The isocyanate blocking reaction can take place at virtually any stage of the PUD synthesis and is usually carried out at temperatures above 30°C. The reaction time varies and depends on the temperature and the type and concentration of the isocyanate, blocking agent, and other components. The blocking reaction can be accelerated by the use of a catalyst. Suitable catalysts include Bronsted bases and / or Lewis acids. Examples include alkali metal alcoholates, phenolates, and metal carboxylates.

[0067] Deblocking may be performed during chain extension, or during polymer drying and / or another cure. In many cases, it is preferred to use a blocking agent that evaporates from the polymer during drying or curing. In these cases, low molecular weight blocking agents such as dimethyl malonate, diethyl malonate, acetoxime, butanone oxime, butylaldoxime, etc. are preferred.

[0068] The blocked isocyanates of the present invention are also referred to as “Functional Latex They may also be used in combination with other crosslinking chemistries as summarized in “J. W. Taylor MA Winnik J. Coatings Tech., Research, v. 1, No. 3, p. 163 (2004) (incorporated herein by reference). These include melamine-based crosslinkers, metal carboxylates, aziridines, carbodiimides, epoxides, unsaturated compounds, acetoacetoxy and ketone functional polymers and additives, enamine and amine crosslinks, isocyanates and self-blocked isocyanates, OH-functional polyesters and acrylates, acid-functional resins, and hydroxyalkylamides.

[0069] In one embodiment involving ketone-hydrazine crosslinking, the amount of ketone crosslinkable functional groups in the polyamide and polymer containing urethane and / or urea linkages is at least 0.05 milliequivalents per gram of the polymer dispersion, or up to about 1 milliequivalent, preferably about 0.05 to about 0.5 milliequivalents per gram of the polymer dispersion, more preferably about 0.1 to about 0.3 milliequivalents. In that embodiment, the ketone groups can be on the polyamide and polymer containing urethane and / or urea linkages, and / or polymers from ethylenically unsaturated monomers. In another embodiment, at least 10, 20, 30, 40, or 50% by weight of the polyamide and polymer containing urethane and / or urea linkages has at least one ketone group chemically bonded to each polyurethane chain of the polyurethane. In another embodiment, the polyamide and polymer comprising a plurality of urethane and / or a plurality of urea bonds in the form of a dispersion further comprises hydrazine and / or hydrazide groups (sometimes in the form of low molecular weight species, sometimes in the form of a polymer having hydrazide groups) in an amount of 10 mol % to about 100 or 200 mol % of the ketone groups in the polyamide and polymer comprising a plurality of urethane and / or a plurality of urea bonds in the form of a dispersion. This provides a ketone chemical reaction with the hydrazine to form a chemical bond that can function as a chemical crosslink. Typically, when adding hydrazine for crosslinking, an excess of hydrazine is not used due to the potentially undesirable reaction of hydrazine with humans. In one embodiment, it is desirable for the amount of hydrazine or hydrazide groups to be about 20 to 100 mol % of the amount of ketone functional groups.

[0070] In one embodiment, the hydrazine and / or hydrazide groups are part of a reactive hydrazine or hydrazide compound (such as adipic dihydrazide) of molecular weight less than 400, 300 or 220 g / mole. In another embodiment, the hydrazide groups are present and are part of a hydrazide-reactive oligomeric or polymeric compound of molecular weight from 300 or 400 g / mole to 500,000 g / mole.

[0071] In another embodiment, the polymer from free radically polymerizable monomers comprises, on average, one or more (more desirably up to about 1 milliequivalent, preferably about 0.05 to about 0.5 milliequivalent, more preferably about 0.1 to about 0.3 milliequivalent per gram of the polymer from free radically polymerizable monomers, based on the weight of the dry polymer) ketone groups per polymer, and the dispersion further comprises hydrazine and / or hydrazide groups in an amount of 10 mol % to about 200 mol %, based on the moles of the ketone groups.

[0072] The ketone-hydrazine crosslinking described above is well known in the art of urethane and acrylic polymer dispersions as an effective crosslinking agent for polymer dispersions near room temperature when volatile bases evaporate and the pH of the solution shifts from slightly basic to neutral or acidic pH. US8,901,244 teaches urethane and related compounds in water that are crosslinked or have increased molecular weight by ketone-hydrazine crosslinking. This technique is sometimes also known as azomethine linkage.

[0073] The polyamide and polymers containing multiple urethane and / or multiple urea linkages in the form of a dispersion may also include anionic, nonionic, or zwitterionic surfactants to aid in colloidal stabilization of the dispersion.

[0074] process Prepolymers of the disclosed polyamides and polymers containing multiple urethane and / or multiple urea linkages are made according to the present invention by forming a prepolymer from the reaction of Zerewitinoff reactive groups with a polyisocyanate in the substantial absence of water (since water reacts with isocyanate groups) and then dispersing the prepolymer in an aqueous medium. This can be done in any of the ways known in the art. Typically, the formation of the prepolymer is done by bulk or solution polymerization of the components of the prepolymer.

[0075] Once the urethane prepolymer mixture is formed, it is dispersed in an aqueous medium, optionally with the dispersed portion incorporated in the prepolymer / polymer, to form a dispersion or solution. Dispersing the prepolymer in an aqueous medium can be done by any conventional technique, in the same way as dispersing polyurethane prepolymers made by bulk or solution polymerization in water. Typically, this is done by combining the prepolymer blend with an aqueous medium while mixing. If solvent polymerization is used, the solvent and other volatile components can be optionally distilled off from the final dispersion. If the prepolymer contains enough water-dispersibility enhancing compounds, such as anionic, cationic, and / or nonionic monomers, to form a stable dispersion without the addition of emulsifiers (surfactants), the dispersion can be made without such compounds, i.e., optionally, substantially free of surfactants less than 200 g / 1 mole weight. The advantage of this approach is that coatings or other products made from polyamides and polymers containing multiple urethane and / or multiple urea linkages without the use of low molecular weight surfactants exhibit lower water sensitivity, often better film formation, and less foaming.

[0076] Other known methods of making aqueous polyurethane dispersions can also be used to make the dispersions of the present invention. Reviews of these can be found in several publications, including D. Dieterich in Progress in Organic Coatings, vol. 9, pp. 281-340 (1981). Examples of processes include:

[0077] Shear mixing - Dispersion of the prepolymer by shear forces using emulsifiers (external emulsifiers such as surfactants or internal emulsifiers having anionic, nonionic, cationic and / or zwitterionic groups as part of or pendant to the polymer backbone and / or as end groups on the polymer backbone).

[0078] Acetone Process - A prepolymer is formed in the presence or absence of acetone, MEK, and / or other polar solvents that are non-reactive with isocyanates and easily distilled. The prepolymer is further diluted in the above solvents as necessary and chain extended with an active hydrogen-containing compound. Water is added to the chain extended polymer and the solvent is distilled off. A variation of this process is to chain extend the prepolymer after dispersion in an aqueous medium.

[0079] Melt dispersion process - an isocyanate-terminated prepolymer is formed and then reacted with excess ammonia or urea to form a low molecular weight oligomer with terminal urea or biuret groups. The oligomer is dispersed in an aqueous medium and chain extended by methylolation of the biuret groups with formaldehyde.

[0080] Ketazine and Ketimine Process - Hydrazines or diamines are reacted with ketones to form ketazines or ketimines. These are added to prepolymers, remaining inert to isocyanates. When the prepolymer is dispersed in water, the hydrazine or diamine is liberated and chain extension occurs as dispersion occurs.

[0081] Continuous process polymerization - forming an isocyanate terminated prepolymer, which is pumped through high shear mixhead(s), dispersed in water, and then chain extended in said mixhead(s), or simultaneously dispersed and chain extended in said mixhead(s). This is accomplished by multiple streams of prepolymer (or neutralized prepolymer), optional neutralizing agent, water, and optional chain extender and / or surfactant.

[0082] Reverse Feed Process - Water and optionally neutralizing agent(s) and / or chain extender amine(s) are charged to the prepolymer under agitation. The prepolymer may be neutralized prior to adding the water and / or diamine chain extender.

[0083] Additives and Applications It may be desirable to include a coalescing aid in the polyamides in the dispersion form of the present disclosure and in the prepolymers and polymers containing multiple urethane and / or multiple urea linkages to help promote the coalescence of the polymer particles with each other and with any solid additives in the composition at the desired temperature. Coalescing aids are also known as solvents or plasticizers, depending on their function. One type of coalescing aid is the free radical polymerizable monomer (vinyl monomer) previously described for the composite polymer blend. Preferred vinyl monomers include methyl methacrylate, butyl acrylate, ethylhexyl acrylate, ethyl acrylate, and styrene. Coalescing solvents include diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dimethyl carbonate, isopropyl alcohol, dibutylene glycol dimethyl ether, and Texanol (isobutyric acid ester of 2,2,4-trimethyl-1,3-pentanediol).

[0084] Neutralizing agents may be used in the dispersions of the present invention and in coating compositions prepared from such dispersions, if desired. The pH of the composition may range from about 7 to about 10 if anionically stabilized. Suitable neutralizing agents include, but are not limited to, alkaline hydroxides such as lithium, sodium and potassium, as well as organic bases such as ammonia and tertiary amines such as triethanolamine, aminomethylpropanol, dimethylethanolamine, trimethylamine, triethylamine morpholine, and mixtures thereof.

[0085] Crosslinking Agent Compounds having at least one crosslinkable functional group can also be incorporated into the polyurea / urethane of the present invention, if desired. Examples of such compounds include carboxyl, carbonyl, amine, hydroxyl, epoxy, acetoacetoxy, olefinic and hydrazide groups, blocked isocyanates, and the like, as well as those having the same groups in protected form that can reverse back to the original groups from which they are derived. Other suitable compounds that provide crosslinking capability include thioglycolic acid, 2,6-dihydroxybenzoic acid, melamine and its derivatives, polyvalent metal compounds, and the like, as well as mixtures thereof.

[0086] The amount of optional compound having crosslinkable functionality in the prepolymer of polyamide and polymer containing multiple urethane and / or multiple urea linkages is typically up to about 1 milligram per gram of final polymer(s) in the polyurethane dispersion on a dry weight basis. The amount of the compound is preferably about 0.05 to about 0.5 milliequivalents, and more preferably about 0.1 to about 0.3 milliequivalents.

[0087] Other additives known to those skilled in the art can be used to aid in the preparation of the dispersions of the present invention. Such additives include surfactants, stabilizers, defoamers, thickeners, leveling agents, antimicrobial agents, antioxidants, UV absorbers, flame retardants, pigments, dyes, etc. These additives can be added at any stage of the manufacturing process.

[0088] The dispersions of the present invention typically have a total solids content of at least about 20 weight percent in one embodiment, at least about 30 weight percent in another embodiment, at least about 40 weight percent in a further embodiment, and about 45 weight percent in yet another embodiment, based on the weight of the total coating composition.

[0089] As a coating composition or adhesive, it can be applied by any conventional method including brushing, dipping, flow coating, spraying, and the like to any substrate including wood, metal, glass, fabric, leather, paper, plastic, foam, and the like.

[0090] The gloss of the coatings and films of the present disclosure can be achieved according to ASTM D523-14. Measurements can be made at geometric angles of 20 degrees, 60 degrees, or 85 degrees. Desirably, the gloss value of a 3 mil (0.076 mm) thick coating at 60 degrees is less than 60, more desirably less than 40, and preferably less than 20. Desirably, such gloss values ​​have relatively low haze values, less than 5, more desirably less than 4 or 3, and preferably less than 2. Conventional silica planarizing agents with a 60 degree gloss of 20 typically result in haze values ​​of more than 5 or 10. Gloss is related to the ability of a surface to reflect more light in a direction that approximates specular reflection than in other directions. Measurements are correlated with visual observations of the shine of a surface made at similar angles. Evaluation of gloss involves other visual aspects of the surface's appearance, such as clarity of image, reflective haze, and texture. Preferred substrates for measuring gloss and haze include cold rolled metal (optionally primed), glass plates, polyester films such as Mylar, and Leneta charts (optionally black if measuring haze).

[0091] The compositions of the present invention and their formulations are useful as self-supporting films, coatings, inks, and adhesives on various substrates with matte or gloss controlled by polyamides from amine repeat units of formulas I-IV. The compositions of the present disclosure are particularly useful for wood and metal coatings, where prior art matte agents often add porosity or permeability to the coating due to contamination of the material, or substrate damage or corroding materials such as water. The compositions of the present disclosure are particularly useful in metal coatings used for transportation vehicles and other original equipment manufacturers, where a low matte, medium matte, or high matte finish contrasts well with high gloss finishes in other areas. The compositions of the present disclosure are particularly useful for transparent or highly transparent substrates, where it is desired to avoid glare and light reflection on other surfaces, or to prevent / obscure the identification of objects on the opposite side of the substrate without reducing the total light transmission through the substrate. These polymers, including polyamides and multiple urethane and / or multiple urea linkages, have high light transmission through the coating, but with sufficient matting, can substantially block / obscure objects on the other side of the substrate, while still allowing substantially all incident light to pass through the coating. Other prior art matting agents use mineral additives to adjust matting, but these mineral additives have a much higher refractive index than the polyamides, and therefore reflect more of the incident light due to the difference in refractive index between the polymer binder and the matting agent.

[0092] Working Example In these examples, the following reagents were used: H12MDI 1,1'-methylenebis(4-isocyanatocyclohexane) as Desmodur® W from Bayer Corporation Hydrogenated Dimer Acid -DA Sebacic Acid-SA Dodecanedioic acid - DDA Caprolactone - CPL 4,4'-Methylenebis(cyclohexylamine)-MHMDA 4,4'-Methylenebis(2-methylcyclohexylamine)-HMDA 1,2-Cyclohexanediamine - CHDA Isophoronediamine - IDA Polyketone diol is the reaction product of 2 moles of levulinic acid, 1 mole of diglycidyl ether of bisphenol A and 0.5 to 0.7 moles of diisocyanate, resulting in coupling. The polycarbonate was Eternacoll PH100, an aliphatic polycarbonate sold by UBE, believed to be about 1000 g / mole molecular weight diol containing repeat units of carbonates including 1,6-hexanediol and 1,5-pentanediol. DMBA is dimethylolbutanoic acid. The acrylate is a blend of 70% by weight methyl methacrylate, 10% by weight ethylene glycol dimethacrylate, and 20% by weight octylacrylamide. TEA is triethanolamine. Hydrazine is H2N=NH2 and is typically available as 35% active material. ADH is adipic dihydrazide and is usually provided undiluted.

[0093] Example of the synthesis of polyketone diol. A polyketone functional oligomer was prepared by combining items 1-3 of the following ingredients in a four-neck flask equipped with a thermometer, overhead stirrer, and nitrogen gas inlet. With stirring and under a nitrogen blanket, the temperature of the reaction mixture was increased to 100-103°C and held at this temperature for 1 hour. The temperature was then increased to 110-114°C and held there for an additional hour. Finally, the reaction mixture was increased to 121-125°C and held at this temperature for 2 hours or until the acid number was <1.0 (mg / g). At this point, item 4 was added as a solvent, followed by item 5 at 90-94°C to effect coupling of the previously made oligomer. The temperature was increased to 116-120°C and held there until the titrated NCO of the resulting product was <0.1% (or essentially zero). The final material was slightly amber in color and had a viscosity of approximately 5,100 cps at 70°C. [Table 6]

[0094] Polyamide 1 4,4'-methylenebis(cyclohexylamine), hydrogenated dimer acid and sebacic acid were added to a 2000 mL stirred reactor under nitrogen and heated to 180° C. Acid Number of Polymer The monomers were reacted until the KOH / g was below 1. The water formed during the reaction was evaporated from the reactor and the reactor was briefly placed under vacuum to remove traces of water. Caprolactone was then charged and reacted for 6 hours. The final product is a yellowish polyamide oligomer. Polyamide 2 4,4'-Methylenebis(2-methylcyclohexylamine), hydrogenated dimer acid, and dodecanedioic acid were added to a 2000 mL stirred reactor under nitrogen and heated to 180 °C. The monomers were allowed to react until the acid number of the polymer was below 1 (mg KOH / g). Water formed during the reaction was evaporated from the reactor and the reactor was briefly placed under vacuum to remove traces of water. Caprolactone was then charged and allowed to react for 6 hours. The final product is a yellowish polyamide oligomer. Polyamide 3 4,4'-Methylenebis(2-methylcyclohexylamine) and caprolactone were added to a 2000 mL stirred reactor under nitrogen and reacted for 12 hours at 180° C. in the presence of titanium octoate (200 ppm titanium(IV) 2-ethylhexyloxide based on the weight of the reactants) catalyst. The final product is a yellowish polyamide oligomer. Polyamide 4 4,4'-Methylenebis(cyclohexylamine), piperazine and dodecanedioic acid were added to a 2000 mL stirred reactor under nitrogen and heated to 180 °C. The monomers were allowed to react until the acid number of the polymer was below 1 (mg KOH / g). Water formed during the reaction was evaporated from the reactor and the reactor was briefly placed under vacuum to remove traces of water. Caprolactone was then charged and allowed to react for 12 hours in the presence of titanium octoate catalyst. The final product is a yellowish polyamide oligomer. Polyamide 5 4,4'-Methylenebis(cyclohexylamine), isophoronediamine and dodecanedioic acid were added to a 2000 mL stirred reactor under nitrogen and heated to 180 °C. The monomers were allowed to react until the acid number of the polymer was below 1 (mg KOH / g). Water formed during the reaction was evaporated from the reactor and the reactor was briefly placed under vacuum to remove traces of water. Caprolactone was then charged and allowed to react for 12 hours in the presence of titanium octoate catalyst. The final product is a yellowish polyamide oligomer. Polyamide 6 1,2-Diaminocyclohexane and dodecanedioic acid were added to a 2000 mL stirred reactor under nitrogen and heated to 180°C. The monomers were allowed to react until the acid number of the polymer was below 1 (mg KOH / g). Caprolactone was then charged and allowed to react for 6 hours. The final product is a yellowish polyamide oligomer.

[0095] Water-based polyurethane dispersion A general procedure for the preparation, dispersion in aqueous media, and chain extension of polyamides and polymers containing multiple urethane and / or multiple urea linkages. The polyamide and polycarbonate were placed in a reactor, heated to 150°C, and mixed until a homogenous mixture was obtained. The estimated molecular weight of each polyamide is shown in Table I. The components of each polyamide are shown in Table II. The reactor was then cooled to 120°C and Desmodur™ W was charged and reacted at 100°C for 30 minutes. After all the acrylate monomers were added to the prepolymer and the reactor was homogenous, the temperature was set to 85°C and DMBA was charged. The dispersion recipe is shown in Table IV. The DMBA was reacted until the theoretical NCO was reached, then the polyketone diol was added. The polyketone diol was reacted until the theoretical NCO was reached. Triethylamine was added to the prepolymer, the batch was cooled to 65-75°C, and dispersed in water to form a dispersion containing 20-30% by weight polymer and 70-80% by weight water. The polyurethane was then chain extended with hydrazine, and the acrylic polymerization was initiated by the addition of t-butyl hydroperoxide, erythorbic acid, and EDTA-iron complex. After 30 minutes of polymerization exotherm, the temperature was increased to 50° C. and maintained until all the monomers had reacted. The final product is a milky white dispersion that forms a low gloss film. [Table 1] [Table 2] [Table 3] [Table 4] The acrylate is a blend of 70% by weight methyl methacrylate, 10% by weight ethylene glycol dimethacrylate, and 20% by weight octylacrylamide. [Table 5]

[0096] Except in the examples or where otherwise indicated, all numerical amounts herein specifying amounts, reaction conditions, molecular weights, number of carbon atoms, etc., are understood to be modified by the word "about." All percentages and formulation values ​​are on a molar basis unless otherwise indicated. All molecular weights are number average molecular weights unless otherwise indicated. Unless otherwise indicated, each chemical or composition referred to herein should be construed to be a commercial grade material that may include isomers, by-products, derivatives, and other such materials that are typically understood to be present in commercial grades. However, unless otherwise indicated, the amount of each chemical component is presented exclusive of any solvents and diluents that may be customarily present in commercially available materials. As used herein, "consisting essentially of" allows for 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"). As used herein, parentheses are used 1) to indicate that something is optionally present, such as monomer(s) meaning one or more monomers, or (meth)acrylate meaning methacrylate or acrylate, 2) to modify or further define the preceding terms, or 3) to recite narrower embodiments.

[0097] 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.

[0098] According to a preferred embodiment of the present invention, for example, the following is provided: (Section 1) A colloidally stabilized polymer dispersion in an aqueous medium, the polymer comprising a polyamide oligomer and a plurality of urethane linkages and / or a plurality of urea linkages, the dispersion in the aqueous medium comprising: a) The following [ka] A polyamide oligomer having an amine repeat unit selected from a polyamide oligomer in which R1-R5 are independently selected from H or a C1-C4 straight or branched chain alkyl group, and in one embodiment at least 80, 90 or 95 mole % of all R5 groups are desirably H, and the nitrogen end group of the amine repeat unit is reacted with a reactive carbonyl repeat unit having at least one carbonyl group capable of forming an amide bond, such as a dicarboxylic acid, lactone, hydroxycarboxylic acid and / or lactam or aminocarboxylic acid; b) at least one repeat unit from a polyisocyanate reacted with a hydroxyl group or an amine group; c) reacting water-dispersible groups to form said polymer containing polyamide and multiple urethane and / or multiple urea linkages; Further, a colloidally stabilized polymer dispersion in an aqueous medium, wherein the amine repeat unit is part of the polymer comprising polyamide and multiple urethane and / or urea linkages, and the amine repeat unit is about 4 to about 15 weight percent of the polymer comprising polyamide and multiple urethane and / or multiple urea linkages. (Section 2) 2. The polymer dispersion in an aqueous medium according to claim 1, wherein the polyamide oligomer has, on average, a total of about 1 to about 10 repeat amine units of Formula I or Formula II per polymer chain (and desirably, the polyamide oligomer is chemically covalently bonded to at least 10 mol % of the polymer). (Section 3) At least one of the amine repeat groups of the polyamide oligomer has the formula: a) —(C(═O)—R 2 —(C(═O)—R 3 —(C(═O)—R 4 —(C(═O)—R 5 —(C(═O)—R 6 —(C(═O)—R 7 —(C(═O)—R 8 —(C(═O)—R 9 —( e The repeating unit -C(=O)- (wherein , R e is C3~C48もしくは58 A linear or branched alkylene group (optionally unsaturated), more preferably a C8-C 38 a) a linear or branched alkylene group (optionally unsaturated) of the formula -C(=O)-R f The repeating unit -O- (wherein R f is C1~C 14 (more desirably C2 to C5) linear or branched alkylene group (optionally unsaturated), or c) a combination thereof. (Section 4) 4. The polymer dispersion according to item 3, wherein the polyamide oligomer is further reacted with a cyclic lactone (preferably caprolactone) or a hydroxycarboxylic acid having 2 to 15 carbon atoms to chain extend the polyamide oligomer with polyester repeat units, the polyester repeat units being 1 to 75% by weight of the polymer comprising polyamide and a plurality of urethane and / or urea bonds. (Section 5) 5. The polymer dispersion of any one of claims 1 to 4, wherein the polymer further comprises a) one or more polyester segments, b) one or more polycarbonate segments, c) one or more polyether segments, or d) a blend thereof chemically bonded to the polymer or physically blended with the polymer of the dispersion, wherein the polyester, polycarbonate, or polyether segment, or blend thereof, optionally has a number average molecular weight of about 500 to 5,000 g / mole, and the segment(s) constitute from about 2, 5, 10, or 15 to about 30, 40, or 50 weight percent of the total polymer weight of the polymer dispersion. (Section 6) 6. The polymer dispersion according to any one of items 1 to 5, further comprising an unsaturated free radically polymerizable monomer reactant or a polymer species derived from the unsaturated free radically polymerizable monomer reactant in an amount of about 10 to about 50% by weight, based on the total weight of the polymer in the dispersion. (Section 7) 7. The polymer dispersion according to any one of claims 1 to 6, further comprising a crosslinking agent or crosslinkable groups incorporated into the polymer that promote crosslinking. (Section 8) The polymer dispersion has the following structure: [ka] and further comprising at least 5 wt. % (more desirably at least 10, at least 15, at least 20 or at least 25 wt. %) of a polyamide having tertiary amide repeat units of In the formula, R a is the alkylene portion of the dicarboxylic acid and is a cyclic, straight or branched chain (optionally containing aromatic groups) alkylene of 2 to 48 or 58 carbon atoms, optionally containing up to 1 heteroatom per 3 or 10 carbon atoms, more preferably 4 to 38 carbon atoms of the diacid; In the formula, R b has 2 to 60 carbon atoms, more preferably 2 to 36, or 2 or a straight or branched chain (optionally being or containing a cyclic, heterocyclic, or aromatic moiety(s)) alkylene group of 4 to 12, more preferably 2 to 6, carbon atoms (optionally containing up to 1 or 3 heteroatoms per 10 carbon atoms); R c and R d are each independently a straight or branched chain alkyl group of 1 to 8 carbon atoms, more preferably 1 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 are linked together to form a straight or branched chain alkylene group of 1 or 2 to 4 carbon atoms. (Section 9) At least 60 mol %, more desirably at least 75 mol %, preferably at least 85 mol % of the repeat units of the tertiary amide structure are cyclic tertiary amide repeat units, the repeat units having the structure [ka] wherein R b has 2 to 6 carbon atoms, and R c and R d are linked together to form a straight or branched chain alkylene group of 1 or 2 to 4 carbon atoms. (Section 10) 10. The polymer dispersion in an aqueous medium according to any one of items 1 to 9, wherein the water-dispersible group according to item 1 is selected from the group consisting of anionic, cationic, nonionic, or a blend thereof. (Section 11) The polymer dispersion according to any one of items 1 to 10, wherein the water-dispersible group according to item 1 is covalently bonded to the at least one polymer of the polymer dispersion or comprises an anionic water-dispersible group synthesized. (Section 12) 12. The polymer dispersion according to item 10 or 11, wherein the anionic water-dispersing group contains a carboxylic acid present at an acid value of about 5 to about 40 mg KOH / g polymer. (Section 13) The polymer dispersion according to claim 9, wherein the water-dispersing group according to claim 1 comprises a non-ionic oligomer covalently attached or synthesized to the at least one polyurethane of the polymer dispersion (more desirably, the non-ionic oligomer is pendantly attached to the polymer comprising a polyamide and a plurality of urethane and / or a plurality of urea linkages). (Section 14) 11. The polymer dispersion according to claim 10, wherein the water-dispersing group comprises a cationic water-dispersing group, and optionally the cationic water-dispersing group comprises a salt of a tertiary amine or a quaternary ammonium group. (Section 15) The polymer is present in an amount of from about 2, 5, 10 or 15 to about 30, 40 or 50 weight percent of the total polymer weight of the polyamide and the polymer including the urethane and / or urea linkages of the dispersion. 15. The polymer dispersion according to any one of items 1 to 14, comprising a polycarbonate segment. (Section 16) 2. The polymer dispersion of claim 1, further comprising at least 10% by weight of a second polymer (not covalently bonded to the polyamide and the polymer comprising urethane and / or urea linkages) based on the total weight of the polymer in the polyamide and the polymer comprising urethane and / or urea linkages in the form of a dispersion, wherein the second polymer has less than 4% by weight of amine repeat units of Formula I and Formula II. (Section 17) The polymer dispersion according to claim 16, wherein at least 50% by weight of the second polymer is present in separate dispersed polymer particles in the aqueous phase, and at least 50% by weight of the separate dispersed polymer particles contain less than 4% by weight of the combined amine repeat units of formula I and formula II. Item 17. The polymer dispersion according to item 16, wherein at least 50% by weight of the second polymer coexists with the polymer containing polyamide and a plurality of urethane and / or a plurality of urea bonds in the polymer particles, and the polymer containing polyamide and a plurality of urethane bonds and / or a plurality of urea bonds has about 4 to about 15% by weight of an amine repeat unit of formula I and / or formula II. (Section 19) 19. The polymer dispersion according to any one of items 16 to 18, wherein the second polymer is a polyurethane polymer. (Section 20) 19. The polymer dispersion according to any one of items 16 to 18, wherein the second polymer is a polymer formed from free-radically polymerizable unsaturated monomer(s). (Section 21) 7. The polymer dispersion of any one of the preceding claims formed into a self-supporting film, coating, or adhesive. (Section 22) 22. The polymer dispersion according to claim 21, which has been converted into a self-supporting film or coating on a substrate by forming into the appropriate shape and evaporating the aqueous medium, wherein the film or coating has a gloss value of less than 20 at 60° (optionally having a haze of preferably less than 5, more preferably less than 2) using a film or coating thickness of 3 mils (76 micrometers) according to ASTM D523-14 using an Elcometer 408. (Section 23) 23. The polymer dispersion according to claim 22, in the form of a coating on a substrate, wherein the substrate is metal, wood, transparent plastic, or transparent glass. (Section 24) The polymer dispersion of any one of the preceding claims, wherein at least 80, 90 or 95 mole percent of the R5 groups of the amine repeat units are H.

Claims

1. A colloidally stabilized polymer dispersion in an aqueous medium, the polymer comprising a polyamide oligomer and a plurality of urethane linkages, or a plurality of urea linkages, or a combination of a plurality of urethane linkages and a plurality of urea linkages, the polymer dispersion in the aqueous medium comprising: a) Below 【Chemistry 1】 A polyamide oligomer having an amine repeat unit selected from Here, R １ ~R ５ are independently H or C １ ~C ４ wherein the nitrogen end group of the amine repeat unit is reacted with a reactive carbonyl repeat unit having at least one carbonyl group capable of forming an amide bond; b) at least one repeat unit from a polyisocyanate reacted with a hydroxyl group or an amino group; c) a polyamide oligomer and water-dispersing groups attached to said polymer that include multiple urethane linkages, or multiple urea linkages, or a combination of multiple urethane linkages and multiple urea linkages; Including, further, wherein the amine repeat unit is part of the polymer comprising a polyamide oligomer and a plurality of urethane linkages, or a plurality of urea linkages, or a combination of a plurality of urethane linkages and a plurality of urea linkages, and the amine repeat unit is 4-15% by weight of the polymer comprising a polyamide oligomer and a plurality of urethane linkages, or a plurality of urea linkages, or a combination of a plurality of urethane linkages and a plurality of urea linkages; and wherein at least one of said amine repeat units of said polyamide oligomer is bonded to a repeat unit of the formula -(C(=O)-R e -C(=O)-, where R e is a C 3 to C 58 linear or branched alkylene group, optionally unsaturated); Polymer dispersions.

2. 2. The polymer dispersion of claim 1, wherein said polyamide oligomer has, on average, from 1 to 10 total said amine repeat units of formula I per polymer chain.

3. At least one of the amine repeat units of the polyamide oligomer has the formula -C(=O)-R ｆ Repeating units of —O— (wherein R ｆ is C １ ~C １４ 2. The polymer dispersion of claim 1, wherein the alkyl group is a straight or branched alkylene group (optionally unsaturated) of the formula:

4. 4. The polymer dispersion of claim 3, wherein the polyamide oligomer is further linked to a polyester repeat unit, wherein the polyester repeat unit is 1 to 75 weight percent of the polymer comprising a polyamide oligomer and multiple urethane linkages, or multiple urea linkages, or a combination of multiple urethane linkages and multiple urea linkages.

5. 5. The polymer dispersion of any one of claims 1 to 4, wherein the polymer further comprises a) one or more polyester segments, b) one or more polycarbonate segments, c) one or more polyether segments, or d) a blend thereof chemically bonded to the polymer or physically blended with the polymer of the dispersion, wherein the polyester, polycarbonate, or polyether segments, or blends thereof constitute 2 to 50 wt% of the total polymer weight of the polymer dispersion.

6. The polymer dispersion of claim 1, further comprising an unsaturated free radically polymerizable monomer reactant or a polymer species derived from the unsaturated free radically polymerizable monomer reactant in an amount of 10 to 50 weight percent based on the total weight of polymer in the dispersion.

7. The polymer dispersion of any one of claims 1 to 4, further comprising a crosslinking agent or crosslinkable groups incorporated into the polymer that facilitate crosslinking.

8. The polymer dispersion according to claim 1, wherein the polymer dispersion has the following structure: 【Chemistry 8】 and further comprising at least 5 wt. % of a polyamide having tertiary amide repeat units of Here, R ａ is a cyclic, straight or branched chain (optionally containing aromatic groups) alkylene of 2 to 58 carbon atoms, optionally containing up to one heteroatom per three carbon atoms of said -C(O)-R a -C(O)-; and Here, R ｂ is a straight or branched chain (optionally being or containing a cyclic, heterocyclic, or aromatic moiety(s)) alkylene group of 2 to 60 carbon atoms (optionally containing up to 1 heteroatom per 10 carbon atoms), and R ｃ and R ｄ are individually a straight or branched chain alkyl group of 1 to 8 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 one of R c and R d is attached to R b at a carbon atom; Polymer dispersions.

9. at least 60 mole percent of the tertiary amide repeat units are cyclic tertiary amide repeat units, 【Chemistry 9】 where R ｂ has 2 to 6 carbon atoms, and R ｃ and R ｄ The polymer dispersion of claim 8, wherein: are linked together to form a straight or branched chain alkylene group of 1 to 4 carbon atoms.

10. The polymer dispersion of claim 1, wherein the water-dispersible groups include anionic water-dispersible groups covalently bonded to at least one polymer of the polymer dispersion.

11. The polymer dispersion of claim 10, wherein the anionic water-dispersing groups comprise carboxylic acids present at an acid number of from 5 to 40 mg KOH / g polymer.

12. The polymer dispersion of claim 9, wherein the water-dispersible group comprises a nonionic oligomer covalently bonded to the plurality of urethane bonds of the polymer dispersion.

13. The polymer dispersion of claim 1, wherein the water-dispersible group comprises a cationic water-dispersible group.

14. The polymer dispersion of any one of claims 1 to 4, wherein the polymer comprises polycarbonate segments of number average molecular weight from 500 to 5,000 present in an amount of 2 to 50 weight percent of the total polymer weight of the polyamide oligomer of the dispersion and the polymer comprising multiple urethane linkages, or multiple urea linkages, or a combination of multiple urethane linkages and multiple urea linkages, wherein the number average molecular weight is determined by gel permeation chromatography.

15. The polymer dispersion of claim 1, further comprising at least 10 wt. % of a second polymer based on a total weight of the polymer comprising a polyamide oligomer in the form of a dispersion and a plurality of urethane linkages, or a plurality of urea linkages, or a combination of a plurality of urethane linkages and a plurality of urea linkages, wherein the second polymer comprises less than 4 wt. % of a compound represented by Formula I and Formula II. 【Chemistry 15】 and having an amine repeat unit of the formula: A polymer dispersion in which R 1 -R 5 are independently selected from H or a C 1 -C 4 straight or branched chain alkyl group, and in which the nitrogen end group of said amine repeat unit is reacted with a reactive carbonyl repeat unit having at least one carbonyl group capable of forming an amide bond.

16. The polymer dispersion of claim 15, wherein at least 50% by weight of the second polymer is present in separate dispersed polymer particles in the aqueous phase, and at least 50% by weight of the separate dispersed polymer particles contain less than 4% by weight of combined amine repeat units of Formula I and Formula II; or wherein at least 50% by weight of said second polymer coexists in the polymer particles with said polymer comprising a polyamide oligomer and a plurality of urethane bonds, or a plurality of urea bonds, or a combination of a plurality of urethane bonds and a plurality of urea bonds, and said polymer comprising a polyamide oligomer and a plurality of urethane bonds, or a plurality of urea bonds, or a combination of a plurality of urethane bonds and a plurality of urea bonds has 4 to 15% by weight of an amine repeat unit of formula I, Polymer dispersions.

17. The polymer dispersion of claim 15 or claim 16, wherein the second polymer is a polyurethane polymer; or wherein said second polymer is a polymer formed from free radically polymerizable unsaturated monomer(s); Polymer dispersions.

18. R of the amine repeat unit ５ The polymer dispersion of any one of claims 1 to 4, wherein at least 80 mole percent of the groups are H.

19. Use of a polymer dispersion according to any one of claims 1 to 18 to form a self-supporting film, coating, or adhesive.

20. A self-supporting film formed from the polymer dispersion of claim 1.

21. The self-supporting film of claim 20, obtainable by forming the polymer dispersion into a suitable shape and evaporating the aqueous medium; wherein the film has a gloss of less than 20 at 60° using an Elcometer 408 and a film or coating thickness of 3 mils (76 micrometers) according to ASTM D523-14.

22. A coating formed from the polymer dispersion of any one of claims 1 to 18.

23. The coating of claim 22, wherein the coating is on a substrate and obtainable by forming the polymer dispersion into a suitable shape and evaporating the aqueous medium; and the coating has a gloss value of less than 20 at 60° using an Elcometer 408 and a film or coating thickness of 3 mils (76 micrometers) according to ASTM D523-14.

24. An adhesive formed from the polymer dispersion of any one of claims 1 to 18.

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