Matte 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 an aqueous polymer comprising a polyamide and a plurality of urethane and / or urea-bonded dispersions, comprising a polyamide segment derived from a cyclic aliphatic or aromatic primary or secondary amine reacted with some form of reactive carbonyl, such as a carboxylic acid. These polyamides unexpectedly impart a texture characterized by lower gloss to the surface of coatings derived from the polymer comprising the polyamide and the plurality of urethane and / or urea-bonded dispersions. [Background technology]

[0002] In the coatings industry, a highly glossy, extremely smooth coating finish is sometimes desired. In other cases, a matte (low-gloss) coating or ink surface is desired, where variations in the coating surface reflect incident light in various directions. Various mechanisms and products have been developed to impart a matte finish to different types of coatings (solvent-based and water-based). The coatings industry demands uniformity and consistent control of the degree of matte finish, as well as the ability to easily adjust the level of matte finish, at every stage of the coating manufacturing and application process.

[0003] Silica with controlled particle size has been widely used to achieve a matte finish. It is thought to work by the silica particles protruding from the coating surface, forming raised areas 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 porous the coating). The porosity of the coating reduces its resistance to various liquids that can discolor, damage, or soften the coating, or react unfavorably with the substrate beneath the coating (such as causing metal corrosion). Additionally, silica has a significantly different refractive index than most binders, adding some opacity to the coating.

[0004] The Applicant had two prior applications (US9,527,961 and US2016 / 009953) that described polyamide-containing polymers and polyurethane dispersions in which a high proportion of the polyamide was a tertiary polyamide derived from piperazine. SUMMARY OF THE INVENTION

[0005] The present invention relates to polyamides derived from specific cycloaliphatic or aromatic primary or secondary amine groups, which impart a low gloss (high matte) finish to coating coatings derived from polymer dispersions in an aqueous medium, in an aqueous medium (e.g., water and optionally water-soluble organics), as well as polymers comprising a plurality of urethane and / or a plurality of urea bond dispersions. These polyamides are useful as segments in the binder of a coating, ink, or adhesive. These polyamides can also be prepared separately from a primary polymer binder (e.g., a second polymer), both in the form of dispersions in an aqueous medium. The polymers comprising polyamides and a plurality of urethane bonds and / or urea bonds can be blended with a second polymer and then the blend dispersed in an aqueous medium. Alternatively, the polymers comprising polyamides and a plurality of urethane and / or a plurality of urea bonds and the second polymer can be separately dispersed in an aqueous medium and then the dispersed particles from each in the aqueous medium blended together. Alternatively, these polymers comprising polyamides may be prepared as a masterbatch optionally containing a second polymer, and the masterbatch blended with one or more other polymer dispersions to produce a binder for a coating, ink, or adhesive. Binder The polymers used can be thermoplastic, thermosetting, or elastomeric, and are generally aqueous dispersions of these resins. A distinctive feature of these polymer dispersions, particularly those containing certain polyamides, is their ability to impart a textured surface to the final coating or ink, which results in a reduced gloss (increased matte) coating or ink finish. The amount of polyamide in the polymer of the coating or ink influences the level of reduced gloss or matte finish achieved. [Modes for carrying out the invention]

[0006] Definitions: We use parentheses to indicate that 1) something exists as needed, such as monomer(s) can mean singular or plural monomers, or (meth)acrylate can mean methacrylate or acrylate; 2) modify or further define the terms used herein; or 3) enumerate narrower embodiments.

[0007] The terms "hydrocarbyl" or "hydrocarbylene" in the context of this invention mean a group having a carbon atom directly bonded to the rest of the molecule and having hydrocarbon or primarily hydrocarbon properties. Such groups include pure hydrocarbon groups, i.e., aliphatic groups, and, if necessary, non-hydrocarbon substituents (including heteroatoms) that do not alter the main hydrocarbon properties of the group. Examples of non-hydrocarbon substituents include hydroxy, nitro, cyano (where the cyano group is bonded via a C atom, and so is the acyl), alkoxy, and acyl groups. Suitable heteroatoms will be obvious to those skilled in the art and include, for example, nitrogen, oxygen, and sulfur.

[0008] The first part of the present 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 (often dicarboxylic acid, hydroxycarboxylic acid, or lactone from hydroxycarboxylic acid), such as a carboxylic acid. In a preferred embodiment, both nitrogen atoms are bonded to the cyclic or aromatic ring without an atom intervening between the nitrogen and the ring. This reaction of the amine and carboxylic acid produces water (or a hydroxyl group in the case of a lactone) and amide bonds as byproducts. The formation of the polyamide segment can be facilitated by removing the byproduct water. Generally, polyamide number-average molecular weights of about 500 to 5,000 g / mol, more preferably about 800 or 1,000 to 3,000 g / mol, are readily processable into the final binder by this technique. The applicant uses polyamide in the sense of two or more amide bonds in an oligomer or polymer. These polyamides may initially be amine, hydroxyl, or carboxylic acid-terminated. Generally, it is desirable to form hydroxyl-terminated groups, as these are conventional end groups for polyurethane precursors.

[0009] In many examples, a slightly excess of diamine relative to the moles of reactive carbonyl and / or carboxyl functional groups is used, resulting in a very low acid value when reacted, consuming virtually all of the available carboxyl groups. Adjusting the stoichiometry of the reactive amine and acid group helps control the molecular weight and the main terminal group. In some embodiments, the sole carboxylic acid group is a hydroxycarboxylic acid or its lactone, which yields hydroxyl-terminated polyamides that form polyurethanes when reacted with polyisocyanates.

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

[0011] Preferred cyclic aliphatic or aromatic and primary or secondary diamine reaction products are those of the following formulas Ib to IVb: [ka] Or a combination of those.

[0012] In the formula, R1 to R5 are independently selected from H or C1 to C4 linear or branched alkyl groups, and in one embodiment, preferably at least 80, 90, or 95% by weight of all R5 groups in the amine repeating unit are H.

[0013] Preferred repeating units of cyclic aliphatic or aromatic and primary or secondary diamines are those of formulas I to IV. [ka] Or a combination of those.

[0014] In the formula, R1 to R5 are independently selected from H or C1 to C4 linear or branched alkyl groups, and in one embodiment, preferably at least 80, 90, or 95% by weight of all R5 groups of the amine repeating unit are H, and at least 80, 90, or 95% by weight of the cyclic aliphatic or aromatic moiety of the molecule are cyclic aliphatic such that formulas 1 and II (preferably) become Ia and IIa as shown below. [ka]

[0015] In the formula, R4 to R1 are independently H or C1 to C4 alkyl groups. In one embodiment, it is used to produce polyamides or amine repeating units of polyamides. In the diamines of formulas Ib-IVb, I-IV, and Ia-IIa, at least 60, 70, or 80 of the R1, R2, R3, and R4 groups are hydrogen. In one embodiment, preferably, at least 80, 90, 95, 99, or 100 mol% of the R5 group is hydrogen, and these primary amines, which are obtained, react to form polyamides. [ka] and [ka] Generate a repeating unit, In the formula, R1 to R4 are as described above. Examples of aliphatic primary cyclic diamines include 1,3-diaminocyclohexyl and 4,4'-methylenebis(cyclohexylamine), optionally substituted mono or dialkyl (methyl preferred) as taught above. While cyclic aliphatic diamines and cyclic aromatic diamines have been shown, aromatic diamines are thought to produce yellow in polymer coatings and inks when exposed to a light source. Therefore, primary aliphatic and / or secondary diamines are slightly preferred.

[0016] The amount of primary and / or secondary diamines having specific aliphatic cyclic or aromatic structures of formulas I to IV, which have amine groups directly bonded to carbon atoms in the cyclic structure incorporated as an amine compound skeleton, is about 1 or 2 to about 20 or 25% by weight of the total polymer in the polymer dispersion, more preferably 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, filler, and pigment).

[0017] In one embodiment, the diacid reacted with the aliphatic cyclic diamine component is a C 10 ~C 40 dicarboxylic acid containing a dicarboxylic acid and a dimer fatty acid and is a C4~C 50または60 dicarboxylic acid. Larger diacids that are particularly preferred include sebacic acid, dodecanedioic acid, and dimer acid. The repeating units derived therefrom have the structure [Chemical formula] wherein Ra is a C2~C 48または58 , more preferably a C8~C 38 hydrocar byl group. Preferred diacids include sebacic acid and C 10 ~C 40 aliphatic diacids. In the present application, dimer and trimer fatty acids are very useful.

[0018] The terms dimer fatty acid (also referred to as 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 monounsaturated 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 materials by distillation. The final product usually contains small amounts of monofatty acids and trimer fatty acids, but mostly consists of dimer fatty acids.

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

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

[0021] The dimer fatty acids 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, specifically more than 80% by weight, and particularly 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, specifically less than 20% by weight, and particularly less than 15% by weight. Furthermore, the dimer and / or trimer fatty acids may preferably contain less than 10% by weight, more preferably less than 6% by weight, specifically less than 4% by weight, and particularly less than 3.5% by weight of monofatty acids (or monomers). All of the above weight percentage values ​​are based on the total weight of the polymerized fatty acids and monofatty acids present.

[0022] Equation HO-C(=O)-R F Preferred hydroxycarboxylic acids having -OH, and formulas derived therefrom [ka] The cyclic lactone is A molecule having 2 to 15 carbon atoms, more preferably 2 to 5 carbon atoms, of the above formula (wherein R f Linear, branched, and cyclic R(s) having 1 to 14 carbon atoms, more preferably 1 to 4 carbon atoms f The structure is included. Various unsubstituted and alkyl-substituted caprolactones and valerolactones are preferred. When starting with a hydroxycarboxylic acid, both the hydroxycarboxylic acid and the lactone derived therefrom are formed with the production of 1 mole of water. Structure-(C(=O)-R f This results in a repeating unit of -O-)-.

[0023] As outlined in the abstract of the present invention, hydroxycarboxylic acids or lactones derived from the acid can be used with or without a dicarboxylic acid (and vice versa) to generate amide bonds, and the polyamides of the present invention can be chain-extended using the lactone or hydroxycarboxylic acid with polyester repeating units. When the polyamide is chain-extended with polyester repeating units from a hydroxycarboxylic acid or a lactone derived therefrom, the amount of polyester repeating units is preferably about 1 to about 75% by weight of the polymer in the polyurethane dispersion.

[0024] The polyamide repeating structure of 1 mole of diacid and 1 mole of a specific primary diamine appears as follows: [ka] The primary diamine components appear as follows: [ka] Diamine R b It appears to be a structure selected from the following groups, [ka] In the formula, R1 to R4 are as described above. If the amine repeating unit is of the secondary amine type having an R5 group other than hydrogen, its structure will have an R5 group on the nitrogen of the amide bond. These repeating units are most common in polyamides, but monofunctional or trifunctional amide-forming products may also exist, as long as at least 50, 70, 80, 90, or 95 mole percent of the amine reactant is bifunctional.

[0025] A second embodiment of the present invention involves a) incorporating or blending a second, third, or more polymers into a) a polymer containing polyamide and multiple urethane and / or urea bonds dispersed in an aqueous medium, or b) preparing separate dispersions of a polymer containing polyamide and multiple urethane and / or urea bonds in an aqueous medium and a second, third, or more polymers (which are then blended as dispersions to form a blend). Formulas I to IV These two steps are desirable because the amount of polyamide having repeating units and polymers containing multiple urethane and / or urea bonds controls the relative amount of mattification or gloss reduction in the final polymer film. The level of mattification or gloss reduction can be controlled by blending two polymers: one polymer containing polyamide having repeating units of formulas I-IV and another polymer(s) substantially lacking repeating units of formulas I-IV. A combination of a) and b) can be used, in which case one second polymer is blended with a polymer containing polyamide and multiple urethane and / or urea bonds before dispersion in an aqueous medium, and a third polymer is made into a separate dispersion in an aqueous medium and then blended with the polymer containing polyamide and multiple urethane and / or urea bonds, as well as the second polymer blended before dispersion in the aqueous medium. The applicants generally use the term "incorporated" to mean covalently bonded to the polyurethane when discussing polymer segments of polyurethane. The applicants generally use the term "blended" to mean forming a physical blend.

[0026] Modifications of the above embodiments of the present invention (to be used in combination as needed) include the option of incorporating a polymer containing a polyamide and multiple urethane and / or multiple urea bonds into a larger polyurethane structure by polymerizing a) esterifying monomer(s) and / or b) other polyamide-forming monomer(s) to the ends of a polyamide chain, or by linking the polyamide to other larger oligomer or polymer species, for example, by the reaction of a Tselevichnov reaction group on an oligomer or polymer species with a polyisocyanate.

[0027] In one embodiment, polyester segments are added to one or both ends of a polyamide polymer by ester polymerization. This can be achieved by adding polyester-forming monomers to the polyamide, catalyzing ester polymerization as needed, 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 number of polyamide segments and the amount of polyester-forming reactants added relative to the reaction conditions. Alternatively, dicarboxylic acids and dihydroxyl compounds can be polymerized in the presence of a polyamide and partially or completely bonded to the polyamide by conventional condensation polymerization.

[0028] Alternatively, polyisocyanate reactants can be used to bond the polyamides from cyclic aliphatic or aromatic and primary or secondary polyamines to other monomers, oligomers, or polymer species by polymerizing different polymer structures directly from monomers or with the polyamides. For example, polyester, polyether, or polycarbonate segments having about two terminal tserevichnov groups per segment can be bonded to polyisocyanates on polyamide segments that provide a matte finish. Polyether, polyester, and polycarbonate segments are preferable to have about two tserevichnov groups per segment, as this is thought to result in linear polymers when the polyisocyanate has about two reactive isocyanate groups per segment. Small amounts of monofunctional or trifunctional reactants can be used, and the results are known to be similar (in particular, the average functional value remains about 2 when the amounts of monofunctional and trifunctional reactants are approximately equal in moles). However, if too many monofunctional or trifunctional reactants are used, the molecular weight of the product may be too low or too high. The Tselevitchinoff group is well known and is defined as an active hydrogen-containing group (such as an amine or hydroxyl, which are the main Tselevitchinoff groups in this disclosure) that reacts with an isocyanate to form a covalent chemical bond called a urea bond or urethane bond. When a urethane bond is formed, the bond consists of a hydroxyl group and an isocyanate. A urea bond is formed when the bond is located between the t groups and between the amine group and the isocyanate group. In a preferred embodiment, the polyester, polyether, and polycarbonate segments having the Tselevitchinov-terminated group have a number-average molecular weight of about 500 to about 5,000 g / mol.

[0029] This number-average molecular weight can be calculated when polyesters, polyethers, and polycarbonates are bifunctional. The number and type of functional groups per polymer segment can be determined by simply dividing the gram weight of the segment in the sample by (0.5 times the number of functional groups expressed in moles in the sample). This number-average molecular weight can also be determined by performing gel permeation chromatography (GPC) in a good solvent such as tetrahydrofuran and calibrating the GPC column with a series of commercially available, known molecular polystyrene calibration samples. Generally, very similar molecular weights are obtained from both methods.

[0030] A series of polyamide oligomers were prepared from conventional bifunctional acids and alicyclic primary diamines. The initial oligomers may contain amine-terminated groups, carboxyl-terminated groups, or other terminal groups derived by reacting the terminal amine or carboxyl group with other reactants. Because these structures have strong hydrogen bonds, they are not easily deformed during film formation, and while theoretical constraints are undesirable, they are thought to facilitate the formation of desired textured coating surfaces with high matte / low gloss finishes when films are formed from aqueous dispersions. This occurs even 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 prepared by condensation reactions of reactive groups on desired monocarboxylic or dicarboxylic acid monomers and alicyclic and / or aromatic primary or secondary diamine monomers. Triamine monomers and tricarboxylic acids are less desirable for this purpose, as they are thought to produce highly branched, indeformable 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 formation of amides by the reaction of carboxylic acid groups with amine groups can be catalyzed by boric acid, boric acid esters, boranes, phosphorous acid, 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 polyamides, including polymers and polyurethane dispersions, in which a high proportion of amide bonds are tertiary amide bonds derived from piperazine and other secondary diamines. These polymers were not matte or low-gloss on their own in coating applications. In one embodiment of the present disclosure, it is desirable to blend (before or after dispersion in an aqueous medium) or incorporate into each other a matte polymer containing the polyamides of the present disclosure and a plurality of urethane and / or urea bonds with the prior tertiary polyamide-containing polymers. This results in varying levels of planarization or gloss reduction in these polyamides. In one embodiment, the polyamide preferably contains 5 to 85% by weight, more preferably at least 10, 15, 20, or 25% by weight and up to about 65% by weight (based on the total weight of polymer(s) in the polyamide-containing polyurethane dispersion in an aqueous medium), wherein the polyamide is characterized as at least 75% by weight of amide repeating units, where at least 60, 75, or 80 mol% of the amide bonds are tertiary amide bonds, where at least 60, 70, or 80% by weight of the amine groups in the amide repeating units are cyclic diamines, where the nitrogen atom is part of the ring, and where there are 3 or 4 to 10 carbon atoms, such as piperazine or mono or dialkyl (C1-C4) substituted piperazine.

[0033] The tertiary polyamides of those previously disclosed materials had lower minimum film-forming temperatures (generally about -10 to about 20, 25, or 30°C) than most polyamides derived from primary amines, allowing them to form films at or near room temperature (about 20–25°C) without the use of large amounts of plasticizers, solvents, or flocculants. The tertiary amide bonds in those disclosures were formed from a covalent bond between a secondary amine and a carboxylic acid group, resulting in the tertiary amide bond (a key aspect of these previous disclosures is obtaining lower minimum film-forming temperatures). Primary amines react with carboxylic acid-type groups to form secondary amides, which generally have higher minimum film-forming temperatures, while other elements remain the same.

[0034] For example, N-methylaminoethanol or HN(R α )(R β In some cases, it is desirable to convert the carboxylic acid-terminal polyamide segment to a hydroxyl (Tselevichinov group) by reacting it with an amino alcohol such as R α R is a C1-C4 alkyl group, β The alcohol group and C2-C 12 Contains an alkylene group, or alternatively R α and R β These are interbonded to form a cyclic structure and a C3-C3 group containing a pendant hydroxyl group (as in 2-hydroxymethylpiperidine). 16 Alkylene groups may be formed, and any of these can form a polyamide with a terminal hydroxyl group. (In contrast to hydroxyl groups) The reaction of a secondary amine with a carboxylic acid may be favorable by using 100% molar excess 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, a polymer comprising a polyamide and a plurality of urethane and / or plurality of urea-bonded dispersions is copolymerized or blended with other polyamide-containing polymer dispersions (described as initial tertiary polyamides) as described in the following paragraphs. Preferred dicarboxylic acids for forming initial tertiary polyamides are those in which the alkylene moiety of the dicarboxylic acid is a cyclic, linear, or branched (optionally including aromatic groups) alkylene of 2 to 36 carbon atoms, more preferably 4, 8, or 12 to 36 carbon atoms, optionally containing up to 1 heteroatom per 3 or 10 carbon atoms (dicarboxylic acids contain 2 more carbon atoms than the alkylene moiety). These include dimer fatty acids, hydrogenated dimer acids, sebacic acids, etc. Generally, the applicants prefer dicarboxylic acids having larger alkylene groups, because dicarboxylic acids generally provide polyamide repeating units at lower film formation temperatures.

[0036] Preferred diamines for forming tertiary polyamides include diamines having 6 to 60 carbon atoms, more preferably 6 to 20, preferably 6 or 12, or 13 to 15, 17 or 20 carbon atoms, optionally containing one heteroatom for every 3 or 10 carbon atoms of the diamine (excluding 2 nitrogen atoms), and optionally containing various cyclic, aromatic, or heterocyclic groups, provided that one or both of the amine groups are primary amines, and preferred formulas are as follows: [ka] R b R is an alkylene group (which may include or contain cyclic, heterocyclic, or aromatic moieties) of 2 to 36 carbon atoms, more preferably 2 or 4 to 12 carbon atoms, with direct bonds, linear or branched chains (which may include or contain cyclic, heterocyclic, or aromatic moieties as needed), and R c and R d Each , a linear or branched alkylene group having 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms, or R as needed c and R d They bond together to form a single linear or branched alkylene group of 1 to 8 carbon atoms, or R as needed. c and R d One of them is a carbon atom and R b It binds to R, and more preferably R c and R d These atoms bond together, forming a combination of 1 or 2-4 carbon atoms.

[0037] In one embodiment of the prior disclosure relating to tertiary polyamides, preferably at least 50% by weight, more preferably at least 60, 70, 80, or 90% by weight of the polyamide oligomer or telechelic polyamide comprises repeating units from a diacid, wherein the diamine structure of the repeating units is as follows: [ka] In the formula, R a This is the alkylene moiety of a dicarboxylic acid, and is a cyclic, linear, or branched (optionally including aromatic groups) alkylene of 2 to 36 carbon atoms, more preferably 4 to 36 carbon atoms, including up to 1 heteroatom per 3 or 10 carbon atoms of the diacid (the diacid form contains 2 more carbon atoms than the alkylene moiety of the diacid). In the formula, R b This is given by the following formula: [ka] In the formula, R b R is 2 to 36 or 60 carbon atoms, more preferably 2 or 4 to 12 carbon atoms, c and R d Each is a linear or branched alkyl group consisting of 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms, or R c and R d They bond together to form a single linear or branched alkylene group of 1 to 8 carbon atoms, or, if necessary, R c and R d One of them is a carbon atom and R b It binds to R, and more preferably R c and R d These atoms bond together to form an alkylene group consisting of 1 or 2-4 carbon atoms.

[0038] During the reaction of polyamide and polyisocyanate according to this disclosure to form a polyamide-containing polyurethane, other species can be present along with the Tserevichnov group to co-react with the resulting polyurethane. These may be low molecular weight species (e.g., diols or diamines less than 500 g / mol) or high molecular weight species (e.g., oligomers of 500-5,000 g / mol added to form a high or low Tg phase in the resulting urethane polymer). Generally, when a low viscosity prepolymer is desired to produce a polymer dispersion in an aqueous medium, only a component having a stoichiometric imbalance between the reactants to form a medium molecular weight species called a prepolymer is reacted with an excess of functional groups that are the main ends of most prepolymer units. This is usually achieved by moving the stoichiometric ratio of isocyanate groups to Tserevichnov groups away from a 1:1 ratio (resulting in an excess of isocyanate or Tserevichnov groups acting as end groups, thus producing a prepolymer with a limited molecular weight). The molecular weight of the prepolymer is Because the viscosity can be kept quite low (5,000 g / mol to 100,000 g / mol), the prepolymer is liquid at room temperature or slightly above room temperature (generally up to about 80°C). This low viscosity below 80°C promotes mixing and shearing of the liquid prepolymer, forming a stable, finely dispersed colloidal prepolymer phase in water. In many cases, an excess of isocyanate groups is used so that the prepolymer has isocyanate ends.

[0039] The molecular weight of a urethane prepolymer can be increased after the prepolymer has been dispersed (or, as may be referred to, chain-extending the prepolymer within the urethane polymer). This can be done by adding low molecular weight species such as diols, triols, tetrols, or diamines, triamines, or tetraamines that can react with isocyanate-terminated prepolymers to the dispersion, thereby linking them to higher molecular weight species. The isocyanate groups of the prepolymer can also react with water in the continuous phase to produce CO2 gas and terminal amine groups on some of the prepolymers. Some amine groups on the prepolymers can then react with the isocyanate groups of other prepolymers, chain-extending both species. The following paragraphs describe the dispersive groups that can be incorporated into prepolymers / polymers, but it is also possible to facilitate the dispersion of prepolymers / polymers in a continuous medium by utilizing anionic, cationic, nonionic, or zwitterionic dispersants and surfactants or mixtures thereof.

[0040] When it is desirable to disperse a prepolymer (or polymer) in a continuous aqueous phase, it is desirable to add surface-active dispersion species such as anionic, cationic, nonionic, or zwitterionic species to the prepolymer (or polymer). These dispersion species help to provide colloidal stabilization to the dispersed phase. When surface-active dispersion groups are incorporated into a polymer, it is desirable to include them in the reaction of the polyamide oligomer or in other sources of Tserevichnov reactive groups (for example, during the preparation of a urethane prepolymer). Dispersion groups having Tserevichnov reactive groups that react with isocyanate groups to form urea or urethane bonds 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 as a surfactant / emulsifier or as a water-dispersing group that can be incorporated into the polyurethane itself. Therefore, to aid in the dispersion of the polymer / prepolymer in an aqueous medium, it is often desirable to include at least one water-dispersibility-enhancing compound, i.e., a dispersion-functional monomer having at least one hydrophilic group, an ionic group or a potentially ionic group, in the reactants for the urethane-forming polymer and prepolymer of the present invention. Typically, this is done by incorporating a compound supporting at least one hydrophilic group, or a group that can be made hydrophilic by chemical modification such as neutralization, into the polymer / prepolymer chain (via one or two Tselevichinov groups of the compound). These compounds may be nonionic, anionic, cationic, zwitterionic, or a combination thereof. For example, an anionic group such as a carboxylic acid group 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. Anionically dispersible urethane prepolymers / polyurethanes based on carboxylic acid groups generally have an acid value of about 1 to about 60 mg KOH / gram, typically 1 to about 40, or even 10 to 35, 12 to 30, or 14 to 25 mg KOH / gram. Other water-dispersibility-enhancing compounds can also be reacted with urethane or urea bonds containing lateral or terminal hydrophilic ethylene oxide or ureide units to form a urethane prepolymer skeleton.

[0042] Particularly interesting water-dispersibility-enhancing compounds are those that can incorporate weak carboxyl groups into prepolymers. Typically, they have the general formula (HO) × Q(COOH) y (In the formula, Q is a linear or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are It is derived from hydroxycarboxylic acids having 1 to 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 mixtures thereof. Dihydroxycarboxylic acids are more preferred, and dimethylolpropanoic acid and dimethylolbutanoic acid are most preferred.

[0043] Another group of particularly interesting water-dispersibility-enhancing compounds are side-chain hydrophilic monomers. Some examples include alkylene oxide polymers and copolymers having alkylene oxide groups with 2 to 10 carbon atoms, as shown in, for example, U.S. Patent No. 6,897,281 (the disclosure of which is incorporated herein by reference). There are commercially available polyethers having two terminal hydroxyl groups near one end of the polyether, which can be incorporated into urethanes and urethane prepolymers as nonionic dispersion moieties. These have a substantial portion of the polyether extending in a manner linked to the urethane from these two bonds at one end of the polyether. These include Tegomer® D3403 and Perstop's Ymer®, as used in U.S. 6,897,381.

[0044] Water-dispersibility-enhancing compounds can impart cationicity to polyurethanes. Cationic polyurethanes contain cationic centers incorporated into or bonded to the backbone. Such cationic centers include ammonium, phosphonium, and sulfonium groups. These groups can be polymerized to the backbone in ionic form or, if necessary, generated by post-neutralization or post-quaternization of the corresponding nitrogen, phosphorus, or sulfur moieties. All combinations of the above groups, and combinations with nonionic stabilization, can be used. Examples of amines include N-methyldiethanolamine and amino alcohols available from Huntsman under the trade name Jeffcat®, such as DPA, ZF-10, Z-110, ZR-50, etc. These 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 improving compounds include thioglycolic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol, and mixtures thereof.

[0046] While the use of water-dispersibility-enhancing compounds is preferred, the dispersion of the present invention can be prepared without them by stabilizing it with a surfactant using a high-shear dispersion method.

[0047] Polyisocyanate Suitable polyisocyanates include aliphatic, alicyclic, aromaticaliphatic, aromatic, and heterocyclic polyisocyanates, as well as their oligomerization products used alone or in mixtures of two or more, having an average of about two or more isocyanate groups per molecule, preferably an average of about two to about four isocyanate groups. Diisocyanates are more preferred. Polyisocyanates are of formula [ka] (In the formula, R Q (wherein Z is a 5-20 carbon atom hydrocarbylene group which optionally contains one or more cyclic aliphatic structures or one or more aromatic rings, and Z is 1-4, more preferably 1-3, and preferably mainly 2 on average.)

[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-dodecanediisocyanate, 2,2,4-trimethyl-hexamethylenediisocyanate, 2,4,4-trimethyl-hexamethylenediisocyanate, and 2-methyl-1,5-pentamethylenediisocyanate. 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-hexamethylenediisocyanate, and 2,4,4-trimethyl-hexamethylenediisocyanate.

[0049] Specific examples of suitable alicyclic polyisocyanates include dicyclohexylmethane diisocyanate (commercially available from Bayer Corporation as Desmodur® W), isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and 1,3-bis-(isocyanatomethyl)cyclohexane. Preferred alicyclic polyisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

[0050] Specific examples of suitable aromatic aliphatic polyisocyanates include m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, 1,4-xylylene diisocyanate, and 1,3-xylylene diisocyanate. A preferred aromatic aliphatic polyisocyanate is tetramethylxylylene diisocyanate.

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

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

[0053] Conventional blends containing other polymers The polymers comprising polyamide and 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 a polymer dispersion by methods well known to those skilled in the art. Generally, the second polymer can be distinguished from the polymers comprising polyamide and multiple urethane and / or multiple urea bonds in the dispersion because it is not covalently bonded to the polymer comprising polyamide and multiple urethane and / or multiple urea bonds, and / or has less than the specified amount of amine repeating units of formulas I and / or II that define the unique polymers of this disclosure. Such polymers, polymer solutions, and dispersions can be found in ASTot. "Resins, Water-Soluble" in: Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons. 3rd Edn., Vol.20, HFMark. This includes the material described in et al. Eds., pp. 207-230 (1982).

[0054] A composite polymer composition that provides better interpenetration of phases (e.g., free radical polymerizable) Polyurea / urethane containing monomers) In one embodiment, ethylenically unsaturated monomers may be used as a solvent for reducing the viscosity of a prepolymer or polymer containing a polyamide and multiple urethane and / or multiple urea bonds during preparation and dispersion, and subsequently for polymerizing unsaturated monomers to form a polymer. Ethylenelycol-unsaturated monomers and other free-radical polymerizable monomers can be polymerized using a conventional free-radical source to form polymers within a polymer containing a polyamide and multiple urethane and / or multiple urea bond particles, and composite polymers can be formed with a dispersion of a polymer containing a polyamide and multiple urethane and / or multiple urea bonds. Vinyl polymers are a general term for polymers derived from a substantial portion of unsaturated monomers, or polymers derived from those monomers. Acrylics are often considered a subset of vinyl and refer to acrylic acid, acrylates (esters of acrylic acid), and alkacrylates such as methacrylate and ethanolacrylate, and polymers derived therefrom. Various styrene and alkyl-substituted styrene-type monomers, such as vinyl esters including divinylbenzene, (meth)acrylonitrile, and vinyl acetate, unsaturated amides such as acrylamide, dienes with 4 to 6 carbon atoms, vinyl monomers having dispersed moieties such as AMP monomers (2-acrylamido-2-methylpropanesulfonic acid), and other vinyl monomers readily copolymerize with acrylic monomers. Additional free-radical polymerizable materials, such as other unsaturated monomers, may be added to vinyl or acrylic monomers for copolymerization. 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 nearly as reactive (and copolymerizable) as ethylenically unsaturated monomers. Dienes are considered ethylenically unsaturated and copolymerize with both a broad category of vinyl monomers and a narrow category of acrylic monomers.

[0055] Polymerization within polyurethane particles can be carried out by forming an aqueous dispersion of a polymer containing polyamide and multiple urethane and / or urea bond composites, and then polymerizing additional monomers by emulsion polymerization or suspension polymerization in the presence of the dispersion. Another method for producing composite polymers is, for example, to include ethylenically unsaturated monomers in a polymer containing polyamide and multiple urethane and / or urea bond in prepolymer form, together with reactants for forming a prepolymer and / or before dispersing the polyurethane prepolymer, and polymerizing these monomers before, during, and / or after dispersing the prepolymer in an aqueous medium. The weight percentage of polymer(s) from free radical polymerizable monomer (or polymer thereof) based on 100 parts of a polymer containing polyamide and multiple urethane and / or multiple urea bond combined with a free radical polymerizable monomer and any additional blend or incorporated polymer is at least 1, 5, or 10 weight percent, preferably 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 dispersions.

[0056] In one approach, the polyamides and polymers containing multiple urethane and / or multiple urea bonds of the present invention, with or without free radical polymerizable monomers (ethylenically unsaturated monomers) acting as diluents (or plasticizers) during prepolymer formation, can be prepared by any of these approaches.

[0057] Expansion of the definition of composite and / or hybrid polymers dispersed in aqueous media The composite (also known as a hybrid composition) contains polyamide and other repeating units in a polymer containing multiple urethane and / or urea bonds (e.g., polyether, polycarbonate, poly This technology allows for the adjustment of the weight percentage of polyamide repeating units relative to polyester segments (polysiloxane, etc.). Therefore, this technology provides several methods for independently controlling the amount of polyamide in composite polyurethane particles, which may affect the polarity or hydrogen bonding of the composite particles, the surface tension of the composite particles, and / or the modulus of elasticity, tensile strength, etc., of the composite polymer at certain critical temperatures.

[0058] By the term composite and / or hybrid, we intend to include a variety of mixtures of polyamide-rich polymer types, such as polyamides and polymers containing multiple urethane and / or multiple urea bonds, with other polymers. Polymers containing polyamide segments may have other comonomers or comonomer segments directly or indirectly linked to the polyamide segments. These comonomers may include polyethers, polyesters, polycarbonates, polysiloxanes, and the like. The composite and / or hybrid polymers in the composite and / or hybrid dispersions have substantially the same particle size range as those disclosed for 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 the form of a dispersion in an aqueous medium at an amount of about 10, 20, or 30 weight percent to about 70, 80, or 90 weight percent of the polyamide and the polymer containing multiple urethane and / or urea bonds. Typically, lowering the water content can save the transport cost of 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 a polymer containing a polyamide and multiple urethane and / or multiple urea bonds, or one of the second or third polymers therein, to enhance the physical properties of the polymer, such as tensile strength and modulus of elasticity. This can be achieved by adding various crosslinking functional groups to the polymer in a dispersion, or by adding another crosslinking component to a polymer containing a polyamide and multiple urethane and / or multiple urea bonds 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 preferred types, respectively.

[0062] Reactive crosslinking moieties of blocked isocyanates (e.g., MEKO) or 1,3-dicarbonyl compounds (e.g., DEM) enable the delivery of two-component performance in a one-component system. Several types of compounds can be used as blocking (also known as protective or masking) agents to provide crosslinking functional groups in urethane polymers and coating compositions. Their function is to temporarily protect isocyanate groups from undesirable reactions. A key requirement for blocking compounds is that their reaction with isocyanates is reversible. When the reaction is reversed, the isocyanate groups are regenerated and become available for further reactions after deblocking. Deblocking reactions can be induced by physical or chemical means, such as high temperature, radiation, vacuum, catalysts, compounds containing active hydrogen, or combinations thereof. Malonates (e.g., DEM) block isocyanate groups from undesirable 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; this is a variation of a blocking compound.

[0063] Examples of reactive crosslinking moieties (including blocking agents) include 1,3-dicarbonyl compounds, oximes and other N-hydroxyl compounds, phenols, alcohols, lactams, and imitation compounds. Examples include dazoles, pyrazoles, acids, mercaptans, imides, secondary amines, cyanoacetates, malononitriles and their derivatives, and sulfites. Preferred reactive crosslinking agents (including blocking agents) are 1,3-dicarbonyl compounds (dicarbonylmethane) (US2,826,526). Examples include acetylacetone and its derivatives, alkyl acetacetates, alkoxyalkyl acetacetates, barbituric acids and their derivatives. The reactive crosslinking moiety can be reacted to form a prepolymer and then a polyurethane, or the reactive crosslinking moiety may be another isocyanate compound / moiety that reacts to crosslink the polyurethane or to bond the polyurethane to a substrate (e.g., a blocked polyisocyanate moiety or a reaction product of a polyisocyanate and a 1,3-dicarbonyl compound).

[0064] Oximes are another group of generally 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 This is possible. R and R' may also include heteroatom-containing groups, including alicyclic, aromatic, and heterocyclic groups. The oxime may be an aldoxime if one or both of R and R' are hydrogen, or a ketoxime if both R and R' are hydrocarbyl groups, preferably alkyl groups having 1 to 12 carbon atoms. Examples of aldoximes include formaldehyde, acetaldehyde, propional oxime, butyraldoxime, and benzaldehyde. Examples of ketoximes include acetoxime, butanone oxime, methyl ethyl ketoxime (MEKO), methyl isobutyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, and acetophenone oxime. 1,3-Dicarbonyl compounds and oximes can be used alone or in combination. They may be partially replaced by 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 their derivatives, such as esters of hydroxybenzoic acid, pyrazoles, 3,5-dimethylpyrazole, dibutylamine, diisopropylamine, piperidine, piperazine, tert-butanol, cyclohexanol, isopropanol, glycerol carbonate, N-hydroxysuccinimide, hydroxypyridine, and esters of hydroxamic acid. When stepwise reactions are desired, a combination of two or more blocking agents, particularly a mixture of blocking agents that deblock at different temperatures, is preferred.

[0066] Isocyanate blocking reactions can be carried out at virtually any stage of PUD synthesis and are typically performed at temperatures above 30°C. Reaction times vary and depend on temperature, as well as the type and concentration of isocyanate, blocking agent, and other components. Blocking reactions can be accelerated by the use of catalysts. Suitable catalysts include Brønsted bases and / or Lewis acids. Examples include alkali metal alcoholates, phenolates, and metal carboxylates.

[0067] Deblocking may be performed during chain extension, polymer drying, and / or other curing. In many cases, it is preferable to use blocking agents that evaporate from the polymer during drying or curing. In these cases, low molecular weight blocking agents such as dimethyl malonate, diethyl malonate, acetoxime, butanoneoxime, and butyraldoxime are preferred.

[0068] The blocked isocyanates of the present invention are also known as “Functional Latex a These may be used in combination with other crosslinkable chemicals, such as those summarized in “and Thermoset Latex Films” JW.Taylor MAWinnik, Coatings Tech., Research, v.1, No.3, p.163 (2004) (incorporated herein by reference). These include melamine crosslinkers, metal carboxylates, aziridines, carbodiimides, epoxides, unsaturated compounds, acetoacetoxy and ketone-functional polymers and additives, enamine and amine crosslinkers, isocyanates and self-blocking isocyanates, OH-functional polyesters and acrylates, acid-functional resins, and hydroxyalkylamides.

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

[0070] In one embodiment, the hydrazine and / or hydrazide group is part of a reactive hydrazine or hydrazide compound (such as adipic acid dihydrazide) with a molecular weight of less than 400, 300, or 220 g / mol. In another embodiment, the hydrazide group is present and is part of a hydrazide-reactive oligomer or polymer compound with a molecular weight ranging from 300 or 400 g / mol to 500,000 g / mol.

[0071] In another embodiment, the polymer from a free radical polymerizable monomer contains, on average, one or more ketone groups per polymer (on a dry weight basis, per gram of the polymer from the free radical polymerizable monomer, more preferably up to about 1 milliequivalent, preferably about 0.05 to about 0.5 milliequivalents, more preferably about 0.1 to about 0.3 milliequivalents), and the dispersion further contains 10 mol% to about 200 mol% of hydrazine and / or hydrazide groups 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 at room temperature, when volatile bases evaporate and the pH of the solution shifts slightly from basic to neutral or acidic. US8,901,244 teaches about urethanes 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 linking.

[0073] Polymers containing polyamides and multiple urethane and / or multiple urea bonds in the form of a dispersion may also contain anionic, nonionic, or zwitterionic surfactants to help colloidalize the dispersion.

[0074] process Prepolymers of polyamides and polymers comprising multiple urethanes and / or multiple urea bonds of the present disclosure are prepared in accordance with the present invention by forming a prepolymer from the reaction of a Tserevichnov reaction group with a polyisocyanate in substantially the absence of water (because water reacts with isocyanate groups), and then dispersing the prepolymer in an aqueous medium. This can be done by any method known in the art. Typically, the formation of the prepolymer is carried out by bulk or solution polymerization of the prepolymer components.

[0075] Once the urethane prepolymer mixture is formed, it is dispersed in an aqueous medium, along with any dispersed portions incorporated into 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 manner as dispersing polyurethane prepolymers produced by bulk polymerization or solution polymerization in water. Typically, this is done by mixing and combining the prepolymer blend and the aqueous medium. If solvent polymerization is used, the solvent and other volatile components can be removed from the final dispersion as needed. If the prepolymer contains water-dispersibility-enhancing compounds, such as anionic, cationic, and / or nonionic monomers, sufficient to form a stable dispersion without the addition of emulsifiers (surfactants), a dispersion can be prepared without such compounds, i.e., substantially free of surfactants of less than 200 g / mol / weight, as needed. The advantage of this approach is that coatings or other products made from polyamides and polymers containing multiple urethanes and / or multiple urea bonds exhibit lower water sensitivity, often better film formation, and less foaming, without the use of low molecular weight surfactants.

[0076] Other known methods for preparing aqueous polyurethane dispersions can also be used to prepare the dispersion of the present invention. Overviews of these methods 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 a prepolymer by shear force using an emulsifier (an external emulsifier such as a surfactant, or an internal emulsifier having anionic, nonionic, cationic, and / or zwitterionic groups as part of the polymer backbone, suspended from the backbone, and / or as terminal groups on the polymer backbone).

[0078] Acetone process – A prepolymer is formed in the presence or absence of other polar solvents that are nonreactive with acetone, MEK, and / or isocyanates and readily distillable. The prepolymer is further diluted in the solvent as needed and chain-extended with an active hydrogen-containing compound. Water is added to the chain-extended polymer and the solvent is removed by distillation. 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 having terminal urea or biuret groups. This oligomer is dispersed in an aqueous medium and the chain is extended by methylation of the biuret groups using formaldehyde.

[0080] Ketazine and Ketimine Process: Hydrazine or diamine is reacted with a ketone to form ketazine or ketimine. These are added to the prepolymer, remaining inert to the isocyanate. When the prepolymer is dispersed in water, the hydrazine or diamine is released, and chain extension occurs as dispersion takes place.

[0081] Continuous process polymerization forms an isocyanate-terminated prepolymer. This prepolymer is pumped through a high-shear mixing head(s) to disperse in water, and then chain-extended in the mixing head(s), or dispersed and chain-extended simultaneously in the mixing head(s). This is achieved by multiple flows consisting of the prepolymer (or neutralized prepolymer), a neutralizer if necessary, water, and a chain extender and / or surfactant if necessary.

[0082] Back-feed process - Water and, if necessary, neutralizing agents and / or chain extender amines are added to the prepolymer under stirring. The prepolymer may be neutralized before adding water and / or diamine chain extenders.

[0083] Additives and Applications It may be desirable to include flocculating agents in the polyamide and prepolymers and polymers containing multiple urethane and / or multiple urea bonds in the form of dispersions of the present disclosure to help promote the aggregation of polymer particles with each other at a desired temperature and with any solid additives in the composition. Flocculating agents are also known as solvents or plasticizers, depending on their function. One type of flocculating agent is the free-radical polymerizable monomer (vinyl monomer) described above for composite polymer blends. Preferred vinyl monomers include methyl methacrylate, butyl acrylate, ethylhexyl acrylate, ethyl acrylate, and styrene. Flocculating solvents include diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dimethyl carbonate, isopropyl alcohol, dibutylene glycol dimethyl ether, and texanol (isobutyrate ester of 2,2,4-trimethyl-1,3-pentanediol).

[0084] Neutralizing agents can be used, if necessary, in the dispersions of the present invention and in coating compositions prepared from such dispersions. The pH of the composition may be in the range of about 7 to about 10 if anionically stabilized. Suitable neutralizing agents include, but are not limited to, alkaline hydroxides, e.g., lithium, sodium, and potassium, as well as organic bases, e.g., ammonia and tertiary amines, e.g., 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 necessary. Examples of such compounds include carboxyl groups, carbonyl groups, amine groups, hydroxyl groups, epoxy groups, acetoacetoxy groups, olefin groups and hydrazide groups, blocked isocyanates, and others having the same groups in protected forms that can reverse to the original groups from which they are derived. Other suitable compounds that provide crosslinking ability include thioglycolic acid, 2,6-dihydroxybenzoic acid, melamine and its derivatives, polyvalent metal compounds, and mixtures thereof.

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

[0087] Other additives well known to those skilled in the art can be used to assist 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, and the like. These additives can be added at any stage of the manufacturing process.

[0088] The dispersion of the present invention typically has 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 yet another 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 to any substrate, including wood, metal, glass, cloth, leather, paper, plastic, foam, etc., by any conventional method, including brushing, dipping, flow coating, spraying, etc.

[0090] The gloss of the coatings and films of this disclosure can be achieved in accordance with ASTM D523-14. Measurements can be taken at geometric angles of 20, 60, or 85 degrees. Preferably, the gloss value of a 3 mil (0.076 mm) thick coating at 60 degrees is less than 60, more preferably less than 40, and most preferably less than 20. Preferably, such gloss values ​​result in relatively low haze values, with a haze value of less than 5, more preferably less than 4 or 3, and most preferably less than 2. Conventional silica planarizers with a 60-degree gloss of 20 typically result in haze values ​​greater than 5 or 10. Gloss is related to a surface's ability to reflect more light in directions closer to specular reflection than in other directions. Measurements correlate with visual observations of the surface's brilliance performed at similar angles. Other visual aspects of the surface's appearance, such as image clarity, reflective haze, and texture, are involved in the evaluation of gloss. Suitable substrates for measuring gloss and haze include cold-rolled metal (primed as needed), glass plates, polyester films such as Mylar, and Leneta charts (black if necessary for measuring haze).

[0091] The compositions and formulations thereof of the present invention are useful as self-supporting films, coatings, inks, and adhesives on a variety of substrates whose matte or gloss is adjusted by polyamides from amine repeating units of formulas I to IV. The compositions of the present disclosure are particularly useful in wood and metal coatings where conventional matting agents often add porosity or permeability to the coating due to contamination of the material or substrate damaging or corrosive materials such as water. The compositions of the present disclosure are particularly useful in metal coatings used by transport vehicles and other OEM manufacturers where low-matte, medium-matte, or high-matte finishes provide a good contrast to high-gloss finishes in other areas. The compositions of the present disclosure are particularly useful in transparent or highly transparent substrates where it is desired to avoid glare and light reflection on other surfaces or to obstruct / obscure the identification of objects on the opposite side of the substrate without reducing the total transmitted light passing through the substrate. These polymers, including polyamides and multiple urethane and / or urea bonds, have high light transmittance through the coating, and sufficient mattification can substantially obscure / blur objects on the opposite 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 the mattification, but these mineral additives have a much higher refractive index than this polyamide and therefore reflect more incident light due to the difference in refractive index between the polymer binder and the matting agent.

[0092] Examples The following reagents were used in these examples. H12MDI, manufactured by Bayer Corporation, contains 1,1'-methylenebis(4-isocyanatocyclohexane) as Desmodur® W. Hydrogenated dimer acid-DA Sebaciate-SA Dodecane dioxide-DDA Caprolactone-CPL 4,4'-Methylenebis(cyclohexylamine)-MHMDA 4,4'-Methylenebis(2-methylcyclohexylamine)-HMDA 1,2-Cyclohexanediamine-CHDA Isophoronediamine-IDA Polyketone diols are reaction products 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 a coupling reaction. The polycarbonate is Eternacoll PH100, an aliphatic polycarbonate sold by UBE, which is thought to be a diol with a molecular weight of approximately 1000 g / mol containing repeating units of carbonate, 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 octyl acrylamide. TEA is triethanolamine. Hydrazine is H2N=NH2 and is usually available as a 35% active substance. ADH is adipic acid dihydrazide and is usually supplied undiluted.

[0093] Synthesis example of polyketone diols. Polyketone functional oligomers were prepared by combining items 1-3 of the following components in a four-necked flask equipped with a thermometer, overhead stirrer, and nitrogen gas inlet. The temperature of the reaction mixture was raised to 100°C-103°C under a nitrogen blanket with stirring and held at this temperature for 1 hour. The temperature was then raised to 110-114°C and held at this temperature for another 1 hour. Finally, the reaction mixture was raised to 121-125°C and held at this temperature for 2 hours or until the acid value was <1.0 (mg / g). At this point, item 4 was added as a solvent, followed by item 5 at 90-94°C to couple the previously prepared oligomer. The temperature was raised to 116-120°C and held at this temperature until the titration 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. The acid value of the polymer was then determined. The monomers were reacted until the KOH concentration fell below 1 mg / g. The water formed during the reaction was evaporated from the reactor, and any remaining trace amounts of water were removed by briefly placing the reactor under vacuum. Caprolactone was then added and the reaction was carried out for 6 hours. The final product was 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 reacted until the acid value of the polymer fell below 1 (mgKOH / g). The water formed during the reaction was evaporated from the reactor, and any remaining water was removed by briefly placing the reactor under vacuum. Caprolactone was then added and the reaction was carried out for 6 hours. The final product was 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 at 180°C for 12 hours in the presence of titanium octanoate (200 ppm titanium(IV) 2-ethylhexyl oxide based on the weight of the reactants) catalyst. The final product was 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 reacted until the acid value of the polymer fell below 1 (mgKOH / g). The water formed during the reaction was evaporated from the reactor, and any remaining water was removed by briefly placing the reactor under vacuum. Caprolactone was then added, and the reaction was carried out for 12 hours in the presence of a titanium octanoate catalyst. The final product was 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 reacted until the acid value of the polymer fell below 1 (mgKOH / g). The water formed during the reaction was evaporated from the reactor, and any remaining trace water was removed by briefly placing the reactor under vacuum. Caprolactone was then added, and the reaction was carried out for 12 hours in the presence of a titanium octanoate catalyst. The final product was 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 reacted until the acid value of the polymer fell below 1 (mgKOH / g). Caprolactone was then added and the reaction was continued for 6 hours. The final product was a yellowish polyamide oligomer.

[0095] Aqueous polyurethane dispersion General procedures for preparing, dispersing in aqueous media, and chain extension polymers containing polyamides and multiple urethane and / or urea bonds. Polyamides and polycarbonates were placed in a reactor and heated to 150°C, and mixed until a homogeneous mixture was obtained. The estimated molecular weights of each polyamide are shown in Table I. The components of each polyamide are shown in Table II. The reactor was then cooled to 120°C, Desmodur® W was added, and the mixture was reacted at 100°C for 30 minutes. All acrylate monomers were added to the prepolymer, and after the reactor was homogenized, the temperature was set to 85°C and DMBA was added. The dispersion recipe is shown in Table IV. The DMBA was reacted until the theoretical NCO was reached, and 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 of polymer and 70–80% by weight of water. Next, the polyurethane chain was extended with hydrazine, and acrylic polymerization was initiated by adding t-butyl hydroperoxide, erythorbic acid, and an EDTA-iron complex. Thirty minutes after the exothermic reaction of polymerization, the temperature was raised to 50°C and maintained until all monomers had reacted. The final product is a milky white dispersion forming 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 octyl acrylamide. [Table 5]

[0096] Except in the examples, or unless otherwise indicated, all numerical quantities in this specification specifying amounts, reaction conditions, molecular weights, number of carbon atoms, etc., should be understood to be modified by the word “approximately.” Unless otherwise indicated, all percentages and formulation values ​​are molar. Unless otherwise indicated, all molecular weights are number-average molecular weights. Unless otherwise indicated, each chemical substance or composition referred to herein should be construed as a commercial-grade material that may include isomers, by-products, derivatives, and other such materials that are commonly understood to be present in commercial-grade materials. However, unless otherwise indicated, the amounts of each chemical component are given excluding any solvents and diluents that may conventionally be present in commercially available materials. Where used herein, “essentially consisting of” allows for the inclusion of substances that do not substantially affect the basic and novel characteristics of the composition under consideration. All embodiments of the invention described herein are intended and can be read from both an open-ended and comprehensive perspective (i.e., using the phrase “containing”) and a closed and exclusive perspective (i.e., using the phrase “consisting of.”). Where used herein, parentheses are used to indicate that 1) something may be present, such as monomer(plural) meaning singular or plural monomer, or (meth)acrylate meaning methacrylate or acrylate; 2) modify or further define the terms herein; or 3) enumerate narrower embodiments.

[0097] While specific representative embodiments and details have been presented 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, wherein the polymer comprises a polyamide oligomer and a plurality of urethane bonds and / or a plurality of urea bonds, and the dispersion in the aqueous medium is a) The following [ka] A polyamide oligomer having an amine repeating unit selected from, In the formula, R1 to R5 are independently selected from H or C1 to C4 linear or branched alkyl groups, and in one embodiment, at least 80, 90, or 95 mol% of all R5 groups are preferably H, and the nitrogen-terminated group of the amine repeating unit reacts with a reactive carbonyl repeating unit (such as a dicarboxylic acid, lactone, hydroxycarboxylic acid, and / or lactam or aminocarboxylic acid) having at least one carbonyl group capable of forming an amide bond, and a polyamide oligomer, b) At least one repeating unit from a polyisocyanate reacted with a hydroxyl group or an amine group, c) A water-dispersible group comprising a polymer which is reacted to form a polyamide and a plurality of urethane and / or plurality of urea bonds, Furthermore, a colloidally stabilized polymer dispersion in an aqueous medium, wherein the amine repeating unit is part of the polymer comprising a polyamide and a plurality of urethane and / or urea bonds, and the amine repeating unit constitutes about 4 to about 15% by weight of the polymer comprising the polyamide and a plurality of urethane and / or a plurality of urea bonds. (Section 2) A polymer dispersion in an aqueous medium according to item 1, wherein the polyamide oligomer has, on average, a total of about 1 to about 10 amine repeating units of formula I or formula II per polymer chain (and preferably the polyamide oligomer is chemically covalently bonded to at least 10 mol% of the polymer). (Section 3) At least one of the amine repeating groups of the polyamide oligomer is a) a dicarboxylic acid with alternating arrangements of the formula -(C(=O)-R e -C(=O)- repeating unit (in the formula) , R e is C3~C48もしくは58 A linear or branched alkylene group (unsaturated if necessary), more preferably C8~C 38 a) a) formula -C(=O)-R f -O- repeating unit (in the formula, R f is C1~C 14 A polymer dispersion in an aqueous medium as described in item 1 above, wherein a linear or branched alkylene group (more preferably C2-C5) (unsaturated as necessary) or a combination thereof is bonded thereto. (Section 4) The polymer dispersion according to item 3, wherein the polyamide oligomer is further reacted with a cyclic lactone (preferably caprolactone) or hydroxycarboxylic acid having 2 to 15 carbon atoms to extend the polyamide oligomer into polyester repeating units, and the polyester repeating units constitute 1 to 75% by weight of the polymer comprising the polyamide and a plurality of urethane and / or urea bonds. (Section 5) The polymer dispersion according to any one of items 1 to 4 above, 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) blends thereof chemically bonded to the polymer or physically blended with the polymer in the dispersion, wherein the polyester, polycarbonate, or polyether segments, or blends thereof, optionally have a number-average molecular weight of about 500 to 5,000 g / mol, and the segment(s) constitute about 2, 5, 10, or 15 to about 30, 40, or 50% by weight of the total polymer weight of the polymer dispersion. (Section 6) The polymer dispersion according to items 1 to 5, wherein the polymer dispersion further comprises an amount of about 10 to about 50% by weight, based on the total weight of the polymer in the dispersion, of an unsaturated free radical polymerizable monomer reaction or a polymer species derived from the unsaturated free radical polymerizable monomer reaction. (Section 7) A polymer dispersion according to items 1 to 6 above, further comprising a crosslinking agent or crosslinkable group incorporated into the polymer to promote crosslinking. (Section 8) The polymer dispersion has the following structure [ka] The present invention further comprises at least 5% by weight (more preferably at least 10, at least 15, at least 20 or at least 25% by weight) of polyamide having tertiary amide repeating units, In the formula, R a However, the alkylene portion of the dicarboxylic acid is a cyclic, linear, or branched (optionally including an aromatic group) alkylene having 2 to 48 or 58 carbon atoms, and optionally contains 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 However, 2 to 60 carbon atoms, more preferably 2 to 36, or 2 or A linear or branched chain of 4 to 12, more preferably 2 to 6 carbon atoms (which may include or be cyclic, heterocyclic, or aromatic moieties) alkylene group (which may include up to 1 or 3 heteroatoms per 10 carbon atoms), R c and R d However, each is a linear or branched alkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbon atoms, or R c and R d They bond together to form a single linear or branched alkylene group of 1 to 8 carbon atoms, or, if necessary, R c and R d One of them is a carbon atom and R b It binds to R, and more preferably R c and R d A polymer dispersion according to any one of items 1 to 6 above, wherein the molecules are bonded together to form a linear or branched alkylene group of 1 or 2 to 4 carbon atoms. (Section 9) At least 60 mol%, more preferably at least 75 mol%, and more preferably at least 85 mol%, of the repeating units of the tertiary amide structure are cyclic tertiary amide repeating units, and the repeating units are structure [ka] It has, in the formula, R b However, it has 2 to 6 carbon atoms, R c and R d A polymer dispersion in an aqueous medium as described in item 8 above, wherein the atoms are bonded together to form a linear or branched alkylene group of 1 or 2 to 4 carbon atoms. (Section 10) A polymer dispersion in an aqueous medium according to items 1 to 9 above, wherein the water-dispersible group described in item 1 above is selected from the group consisting of anionic, cationic, nonionic, or a blend thereof. (Section 11) A polymer dispersion according to any one of items 1 to 10, wherein the water-dispersible group described in item 1 above is covalently bonded to at least one polymer in the polymer dispersion or comprises a synthesized anionic water dispersion. (Section 12) The polymer dispersion according to item 10 or 11, wherein the anionic aqueous dispersion 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 item 9, wherein the water-dispersible group described in item 1 above comprises a nonionic oligomer covalently bonded to or synthesized to at least one polyurethane of the polymer dispersion (more preferably, the nonionic oligomer is pendant-like to the polymer comprising a polyamide and a plurality of urethane and / or plurality of urea bonds). (Section 14) The polymer dispersion according to item 10, wherein the water-dispersible group comprises a cationic water-dispersible group, and optionally the cationic water-dispersible group comprises a salt of a tertiary amine or a quaternary ammonium group. (Section 15) The polymer is present in the dispersion in an amount ranging from about 2, 5, 10, or 15 to about 30, 40, or 50% by weight of the total polymer weight of the polymer, which includes polyamide and multiple urethane and / or multiple urea bonds, with a molecular weight of 500 to 5,000 g / mol. A polymer dispersion according to any one of items 1 to 14 above, comprising a polycarbonate segment. (Section 16) A polymer dispersion according to any one of the preceding items, further comprising at least 10% by weight of a second polymer (not covalently bonded to the polymer containing the polyamide and multiple urethane and / or multiple urea bonds) based on the total weight of the polymer in the polymer containing the polyamide and multiple urethane and / or multiple urea bonds, wherein the second polymer has less than 4% by weight of amine repeating units of formulas I and II. (Section 17) The polymer dispersion according to item 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 contains less than 4% by weight of combined amine repeating units of formulas I and II. (Item 18) The polymer dispersion according to item 16, characterized in that 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 and / or a plurality of urea bonds has about 4 to about 15% by weight of amine repeating units of formula I and / or formula II. (Section 19) A polymer dispersion according to any one of items 16 to 18, wherein the second polymer is a polyurethane polymer. (Section 20) The polymer dispersion according to any one of the above items 16 to 18, wherein the second polymer is a polymer formed from a free radical polymerizable unsaturated monomer(s). (Section 21) A polymer dispersion according to any one of the preceding items, formed on a self-supporting film, coating, or adhesive. (Section 22) A polymer dispersion according to item 21, which is formed into the appropriate shape and converted into a self-supporting film or coating on a substrate by evaporation of the aqueous medium, wherein the film or coating has a gloss of less than 20 at 60° (optionally having a haze of less than 5, more preferably less than 2) when using an Elcometer 408 with a film or coating thickness of 3 mil (76 micrometers) according to ASTM D523-14. (Section 23) A polymer dispersion according to item 22 above, which is in the form of a coating on a substrate, wherein the substrate is metal, wood, transparent plastic, or transparent glass. (Section 24) A polymer dispersion according to any one of the preceding items, wherein at least 80, 90, or 95 mole percent of the R5 groups of the amine repeating unit are H.

Claims

1. A colloidally stabilized polymer dispersion in an aqueous medium, wherein the polymer comprises 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 the polymer dispersion in the aqueous medium is a) Below 【Chemistry 1】 A polyamide oligomer having an amine repeating unit selected from, Here, R １ ~R4 independently H or C １ ~C ４ A polyamide oligomer selected from a linear or branched alkyl group, where R5 is H, and the nitrogen-terminated group of the amine repeating unit reacts with a reactive carbonyl repeating unit having at least one carbonyl group capable of forming an amide bond; b) at least one repeating unit from a polyisocyanate reacted with a hydroxyl group or an amino group; c) A polyamide oligomer and a water-dispersible group bonded to the polymer comprising a plurality of urethane bonds, a plurality of urea bonds, or a combination of a plurality of urethane bonds and a plurality of urea bonds; Includes, Furthermore, the amine repeating unit is part of the 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 the amine repeating unit is 4 to 15% by weight of the 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 Here, at least one of the amine repeating units of the polyamide oligomer is of the formula -(C(=O)-R ｅ -C (=O)- repeating unit (where R ｅ is C ３ ~C ５８ It is bonded to a linear or branched alkylene group (unsaturated if necessary), Polymer dispersion.

2. The polymer dispersion according to claim 1, wherein the polyamide oligomer has, on average, a total of 1 to 10 amine repeating units of formula I per polymer chain.

3. At least one of the amine repeating units of the polyamide oligomer is of the formula -C(=O)-R ｆ -O- repeating unit (wherein R ｆ is a linear or branched alkylene group (optionally unsaturated) of C １ to C １４ bonded thereto), the polymer dispersion according to claim 1.

4. The polymer dispersion according to claim 3, wherein the polyamide oligomer is further bonded to polyester repeating units, wherein the polyester repeating units constitute 1 to 75% by weight of the polymer, which includes the 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.

5. The polymer dispersion according to 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 in the dispersion, wherein the polyester, polycarbonate, or polyether segments, or a blend thereof, constitute 2 to 50% by weight of the total polymer weight of the polymer dispersion.

6. The polymer dispersion according to claim 2, wherein the polymer dispersion further comprises 10 to 50% by weight of an unsaturated free radical polymerizable monomer reaction product or a polymer species derived from the unsaturated free radical polymerizable monomer reaction product, based on the total weight of the polymers in the dispersion.

7. A polymer dispersion according to any one of claims 1 to 4, further comprising a crosslinking agent or crosslinkable group incorporated into the polymer to promote crosslinking.

8. A polymer dispersion according to any one of claims 1 to 4, wherein the following structure 【Transformation 8】 The present invention further comprises at least 5% by weight of a polyamide having tertiary amide repeating units, Here, R ａ However, it is a cyclic, linear, or branched alkylene (including an aromatic group as needed) having 2 to 58 carbon atoms, and as needed, the -C(O)-R ａ -C(O)- contains at most one heteroatom for every three carbon atoms, and Here, R ｂ However, it is a linear or branched chain of 2 to 60 carbon atoms (which may include or contain cyclic, heterocyclic, or aromatic moieties as needed), an alkylene group (which may contain up to one heteroatom per 10 carbon atoms as needed), and R ｃ and R ｄ However, each is either a linear or branched alkyl group of 1 to 8 carbon atoms, or R ｃ and R ｄ They bond together to form a single linear or branched alkylene group of 1 to 8 carbon atoms, or R ｃ and R ｄ One of them is a carbon atom R ｂ Join, Polymer dispersion.

9. At least 60 mol% of the tertiary amide repeating units are cyclic tertiary amide repeating units, and the structure 【Chemistry 9】 It has, and here, R ｂ However, it has 2 to 6 carbon atoms, and R ｃ and R ｄ The polymer dispersion according to claim 8, wherein the molecules are bonded together to form a linear or branched alkylene group of 1 to 4 carbon atoms.

10. The polymer dispersion according to claim 1, wherein the water-dispersible group comprises an anionic water-dispersible group covalently bonded to at least one polymer of the polymer dispersion.

11. The polymer dispersion according to claim 10, wherein the anionic water-dispersible group contains a carboxylic acid present at an acid value of 5 to 40 mg KOH / g polymer.

12. The polymer dispersion according to 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 according to any one of claims 1 to 4, wherein the water-dispersible group includes a cationic water-dispersible group.

14. The polymer dispersion according to any one of claims 1 to 4, wherein the polymer comprises a polycarbonate segment having a number average molecular weight of 500 to 5,000, present in an amount of 2 to 50% by weight of the total polymer weight of the polymer comprising a polyamide oligomer in the dispersion 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, wherein the number average molecular weight is determined by gel permeation chromatography.

15. A polymer dispersion according to claim 1, further comprising at least 10% by weight of a second polymer based on the total weight of the polymer, which comprises a polyamide oligomer in dispersion form 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, wherein the second polymer comprises less than 4% by weight of formulas I and II. 【Chemistry 15】 It has an amine repeating unit, Here, R １ ~R ５ However, independently, H or C １ ~C ４ A polymer dispersion comprising a linear or branched alkyl group selected, wherein the nitrogen-terminated group of the amine repeating unit reacts with a reactive carbonyl repeating unit having at least one carbonyl group capable of forming an amide bond.

16. A polymer dispersion according to 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 contains less than 4% by weight of combined amine repeating units of formulas I and II, or Herein, at least 50% by weight of the second polymer coexists with the polymer, which contains 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 in the polymer particles, and the polymer, which contains 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, is characterized in that it has 4 to 15% by weight of amine repeating units of formula I. Polymer dispersion.

17. A polymer dispersion according to claim 15 or claim 16, wherein the second polymer is a polyurethane polymer, or Here, the second polymer is a polymer formed from a free radical polymerizable unsaturated monomer(s). Polymer dispersion.

18. Use of a polymer dispersion according to any one of claims 1 to 17 for forming a self-supporting film, coating, or adhesive.

19. A self-supporting film formed from a polymer dispersion according to any one of claims 1 to 17.

20. A self-supporting film according to claim 19, which can be obtained by forming the polymer dispersion into a suitable shape and evaporating the aqueous medium; the film having a gloss of less than 20 at 60° when using an Elcometer 408 with a film or coating thickness of 3 mil (76 micrometers) according to ASTM D523-14.

21. A coating formed from a polymer dispersion according to any one of claims 1 to 17.

22. A coating according to claim 21, wherein the coating is obtained by having the polymer dispersion on a substrate and forming it into a suitable shape and evaporating the aqueous medium; the coating having a gloss of less than 20 at 60° when using an Elcometer 408 with a film or coating thickness of 3 mil (76 micrometers) according to ASTM D523-14.

23. An adhesive formed from a polymer dispersion according to any one of claims 1 to 17.

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