Reactive compositions containing acidic functional compounds and compositions derived therefrom

Abstract

structure: [Chemistry I] JPEG2026520866000041.jpg1934 A reactive composition comprising a first compound having 1 to 12, for example, 1 to 10, or 1 to 6, or 1 to 5, or 1 to 4 carboxylic acid functional groups, wherein R 1 However, it can be a C1-C6, for example, a C1-C4 or C1-C3 linear or branched alkyl group, where X is O, S, or NR 2 It can be, R 2 A reactive composition in which the carboxylic acid functional group can be H, methyl, ethyl, propyl, or isopropyl. The reactive composition also comprises a second compound containing a reactive functional group with respect to the carboxylic acid functional group in the first compound. Compositions derived from the reactive composition, as well as methods for preparing and using the reactive composition and compositions derived therefrom, are also disclosed.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to the following U.S. provisional applications filed under Section 119 of the U.S. Patent Act: 63 / 644,078, filed on 8 May 2024, entitled “Reactive Compositions That Include Acid Functional Compounds and Compositions Derived Therefrom”; 63 / 502,003, filed on 12 May 2023, entitled “Curable Compositions Based on High Acid Value Polyurethanes”; 63 / 501,999, filed on 12 May 2023, under Section 119 of the U.S. Patent Act, entitled “Curable Compositions Based on High Acid Value Resins Using Acid Cure Mechanisms”; and 63 / 502,014, filed on 12 May 2023, entitled “Curable Compositions Based on High Acid Value Resins Using Hybrid Cure Mechanisms”; all of which are incorporated herein by reference.

[0002] field This disclosure generally relates to compositions comprising acidic functional compounds and compositions derived therefrom. [Background technology]

[0003] Reactive compositions and compositions derived therefrom are used in many industrial, construction, and pharmaceutical applications. As a non-limiting example, if reactive compositions are curable, they can be used as coatings, adhesives, and sealants for a wide variety of industrial applications, such as automotive, protective, marine, commercial transport, consumer electronics, and many other applications for decorative and functional purposes. [Overview of the project]

[0004] The present disclosure relates to a reactive composition comprising a first compound having from 1 to 12, such as from 1 to 10, or from 1 to 6, or from 1 to 5, or from 1 to 4 carboxylic acid functional groups according to Structure (I): [Chemical formula] wherein R 1 can be a C1-C6, such as C1-C4, or C1-C3 linear or branched alkyl group, X can be O, S, or NR 2 and R 2 can be H, methyl, ethyl, propyl, or isopropyl. The reactive composition also includes a second compound containing a functional group reactive with the carboxylic acid functional group in the first compound.

[0005] The present disclosure also provides a composition derived from the reactive composition, as well as methods of making and using the reactive composition and the composition derived therefrom.

Embodiments for Carrying Out the Invention

[0006] For the purposes of the following detailed description, it is to be understood that the present disclosure contemplates various alternative variations and orders of steps, unless explicitly specified to the contrary. Further, unless otherwise indicated, except for any examples, all numerical values representing amounts of components used herein and in the claims are to be understood as being modified by the term "about" in all instances. Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the reported number of significant digits and by applying ordinary rounding techniques.

[0007] I. Definition Although the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values ​​described in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error that inevitably arises from the standard deviation observed in their respective test measurements.

[0008] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges contained within it. For example, the range "1 to 10" is intended to include all subranges between (and including) the stated minimum value of 1 and the stated maximum value of 10, i.e., the minimum value equal to or greater than 1 and the maximum value equal to or less than 10.

[0009] In this application, unless otherwise specified, the use of the singular includes the plural, and the plural includes the singular. In addition, in this application, unless otherwise specified, the use of "or" means "and / or," even if "and / or" may be explicitly used in certain cases. Furthermore, in this application, the use of "one (a)" or "one (an)" means "at least one" unless otherwise specified. For example, "one polymer," "one acid," etc., refer to one or more of any of these items.

[0010] Unless otherwise specified, ambient temperature and pressure conditions are ambient temperature (20-25°C, e.g., 23°C) and standard pressure of 101.3 kPa (1 atmosphere) with relative humidity in air between 35% and 75%, e.g., 55%.

[0011] As used herein, “acid value on solid” refers to the quantified acidity of a given chemical substance, based on the milligrams (mg) of potassium hydroxide (KOH) required to neutralize the acidic component in one gram of non-volatile component, according to ASTM D4662-15.

[0012] As used herein, “chemical radiation” refers to electromagnetic radiation capable of initiating photochemical reactions, including but not limited to UVB and UVC radiation (180–315 nm), and nearly UV radiation energies in the range of 320–380 nm (or 400 nm).

[0013] As used herein, the term “adhesive” refers to a substance applied to the surface of one or both of two separate substrates that binds them together and resists their separation.

[0014] As used herein, “Ambient Reactive Extrusion” (“ARE”) and similar terms refer to an additive process in which layers of material, such as a curable composition, are constructed to create a three-dimensional part, such as a three-dimensional article, by coating a layer on top of a layer of curable composition. ARE may use a co-reactive composition, i.e., in non-limiting examples, at least two components that react with each other (i.e., are “co-reactive”), such as a first compound containing a carboxylic acid functional group and a second compound containing a functional group reactive with the carboxylic acid functional group, which react chemically with each other to form a curable composition when extruded in combination and / or successively. The curable composition may then be cured under curing conditions, e.g., exposure to heat, chemical radiation, catalyst, addition of a curing agent after extrusion, etc., to form a product containing a portion of a manufactured article.

[0015] As used herein, “amine” refers to an intramolecular group that generally conforms to structure-NR2, where each R can independently be either an H or a carbon-based group. When both R groups are H, the amine is a “primary amine,” when one of the R groups is H, the amine is a “secondary amine,” and when both R groups are carbon-based groups, the amine is a “tertiary amine.”

[0016] As used herein, the term "ASTM" refers to the publications of ASTM International, West Conshohocken, PA.

[0017] As used herein, the term "aziridine" refers to a molecule containing one or more heterocyclic three-membered ring moieties, each containing one nitrogen atom.

[0018] As used herein, the terms “backbone” and “polymer backbone” refer to the backbone of the monomer “repeating units” that constitute the backbone of a polymer.

[0019] As used herein, the terms “blocked group” or “blocked” refer to reacting a functional group with a molecule to produce a derivative of the functional group that can be reversed, thereby generating the original functional group. Blocked groups can be used, in non-limiting examples, to reduce the activity of a group in a one-component system in order to extend its shelf life. A non-limiting example of a blocked group is reacting a carboxylic acid group with a lower alkyl alcohol to provide a corresponding ester.

[0020] As used herein, the term “base molecule” or similar terms refer to a nonpolymeric carbon-based molecule which may optionally contain heteroatoms that may include pendant functional groups.

[0021] As used herein, "carbodiimide" refers to a molecule containing the substructure: -N=C=N-. "Polycarbodiimide" refers to a molecule having more than one such substructure.

[0022] As used herein, “catalyst” refers to a substance that increases the rate of a chemical reaction without undergoing any permanent chemical change itself.

[0023] As used herein, “chiral center” refers to an atom in a low molecular weight molecule (less than 2,000 g / mol) that has four different atoms or groups bonded to it. If a molecule contains multiple chiral centers and all of them have opposite R / S configurations between two “stereoisomers” (same molecular formula, same bonding, different arrangement of atoms in space), they are “enantiomers.” If at least one (but not all) of the chiral centers are opposite between two stereoisomers, they are “diastereomers.” Enantiomers are mirror images of each other and cannot be superimposed, while diastereomers are not mirror images of each other and cannot be superimposed. A “racemic mixture” is a 50:50 mixture of two enantiomers.

[0024] As used herein, the term “coating” refers to a finished product obtained by applying one or more coating compositions to a substrate to form a coating, as a non-limiting example of curing. A primer coat, base coat or color coat layer, and a clear coat layer may be part of a coating. As used herein, the term “coating layer” is used to refer to the result of applying one or more coating compositions to a substrate in one or more applications of such one or more coating compositions. As a non-limiting example, a single coating layer called a “color coat” or “top coat” may be used to provide both the functions of a base coat and a clear coat and may include the result of applying two or more color coat coating compositions.

[0025] As used herein, the term "coating composition" refers to a composition that forms a protective and / or decorative layer on a substrate and may be a one-component, two-component, or multi-component composition.

[0026] As used herein, the term “colorant” refers to, but is not limited to, any substance that imparts color and / or other opacity and / or other visual effects to a coating composition, and may include dyes and pigments.

[0027] As used herein, the transitional phrase “comprising” (and other equivalent terms, e.g., “containing” and “including”) is “non-exclusive” and is not limited to encompassing an unspecified number of things. Although described in terms of “containing,” the terms “essentially consisting of” and “consisting of” are also within the scope of this disclosure.

[0028] As used herein, the terms “crosslinker” and “crosslinking agent” are used interchangeably to refer to molecules or polymers containing functional groups that are reactive with the crosslinking functional groups of polymers and / or resins in a coating composition.

[0029] As used herein, the term “crosslinking functional group” and similar terms refer to functional groups located within the molecule or backbone of a polymer, often hanging from the polymer backbone, and positioned terminally on the polymer backbone, or combinations thereof, such functional groups can react with other crosslinking functional groups or separate crosslinking agents during curing to produce a crosslinked coating.

[0030] As used herein, terms such as “curable” and “curing” mean, in a non-limiting example, when used in relation to a coating composition, that, in a non-limiting example, at least a portion of the components constituting the coating composition are polymerizable and / or crosslinkable via covalent bonding reactions when exposed to high temperatures or ultraviolet light.

[0031] As used herein, the terms “cyclic compound” and “cyclic portion” refer to a molecule or part of a molecule in which one or more sets of atoms within the molecule are linked together to form a ring.

[0032] As used herein, the term “dye” refers to a coloring substance, often an organic compound, that can be chemically bonded to a substrate or another component in a coating composition.

[0033] As used herein, the term “curing agent” refers to a compound that can participate in chemical reactions resulting in crosslinking and / or polymerization between monomers, oligomers, and / or polymers.

[0034] As used herein, the term “elastomer” refers to a material that may contain long-chain molecules (with a length of at least 100 carbon atoms) or polymers that can recover at least a portion of their original shape after being stretched.

[0035] As used herein, the term “end group” refers to a functional group located at the end of a polymer backbone or at the end of an aliphatic chain.

[0036] As used herein, the term “epoxy” refers to a molecule containing one or more glycidyl or oxirane groups. The term “diepoxy” refers to a molecule containing two epoxy groups. The term “epoxy-terminated compound” refers to a molecule in which the epoxy groups are at the ends of the molecule. Epoxy equivalents (EEW) can be determined according to ASTM D1652-11(2019) and may be reported as g / eq unless otherwise indicated.

[0037] As used herein, the term “filler” refers to a substance that is solid at ambient temperature and added to a variety of materials such as coatings, adhesives, sealants, plastics, rubber, glass, and / or metals, which can be applied, molded, and / or enhance certain properties of the material, while ensuring the stability of the material. Non-limiting examples of fillers include minerals such as calcium carbonate, silica, clay, kaolin, and carbon black.

[0038] As used herein, the terms “flash” or “flash-off” refer to the removal of a solvent that allows the applied coating composition to remain in a liquid state and evaporate.

[0039] As used herein, the terms “free radical catalyst” and “free radical initiator” refer to compounds that decompose into free radicals and initiate a reaction. Non-exclusive examples of free radical initiators include azo initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), peroxides such as benzoyl peroxide (BPO), and redox initiators such as persulfates. Suitable chemiradioactivators or photoinitiators include, but are not limited to, the (Norrish) type I and type II photoinitiators available from IGM Resins under the trade name OMNIRAD.

[0040] As used herein, the term “heteroatom” and similar terms refer to atoms along the main chain of a carbon-based molecule or polymer that are not carbon, including, in non-limiting examples, oxygen in a polyether molecule or sulfur in a thioether molecule.

[0041] As used herein, the term "(hydroxylalkyl)urea" refers to a molecule comprising a single urea group, at least two hydroxyl groups, and having at least two carbon atoms positioned between each of the urea and hydroxyl groups.

[0042] As used herein, the term “hydroxyl-functional compound” refers to an organic compound containing one or more hydroxyl (-OH) groups.

[0043] As used herein, the terms "isocyanate equivalent" and "NCO equivalent" refer to isocyanate (NCO) equivalents (grams per equivalent, g / eq) determined using ASTM D2572-19 (Standard Method for Isocyanate Groups in Urethane Materials or Prepolymers) as revised herein, unless otherwise specified.

[0044] As used herein, the term "isocyanate-reactive compound" refers to, but is not limited to, a molecule containing at least one group that is reactive with an isocyanate group, such as a hydroxyl, primary or secondary amine, and / or thiol.

[0045] As used herein, the term "low molecular weight molecule" refers to a molecule that does not conform to the definition of a polymer or oligomer and typically has a molecular weight of less than 2,000 g / mol.

[0046] As used herein, the term “mercaptopropionic acid” refers to either or both 3-mercaptopropionic acid and 2-mercaptopropionic acid, unless otherwise specified.

[0047] As used herein, the term "(meth)acrylate" and similar terms refer to molecules and parts derived from acrylic acid, acrylate ester, methacrylic acid, methacrylate ester, or both.

[0048] Unless otherwise specified, as used herein, the term “molecular weight” refers to the weight-average molecular weight ("Mw") determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. Where a number-average molecular weight ("Mn") is specified, the weight is determined in the same GPC manner, while calculating the number average from the polymer molecular weight distribution data thus obtained. Mn refers to the total weight of the material divided by the number of molecules in the material, and can be determined using gel permeation chromatography. Unless otherwise specified, Mw and Mn are in units of g / mol.

[0049] As used herein, the term “monomer” refers to a molecule that can react with other monomer molecules through a polymerization process to form a larger polymer chain or three-dimensional network.

[0050] As used herein, the terms “multicomponent,” “multi-K,” and “multi-pack” refer to a coating composition comprising a first component containing a crosslinkable resin, a second component containing a crosslinking agent, and additional components which may or may not contain a crosslinkable resin or crosslinking agent, and these components are kept separate until immediately before use. The crosslinkable resin and crosslinking agent can react when combined to form a thermosetting composition. If a multicomponent coating composition does not contain additional components, it is a two-component or 2-K coating composition.

[0051] As used herein, the terms “one component,” “1-K,” and “1-pack” refer to a coating composition in which all coating components are maintained in the same package after manufacturing, during shipping and storage, and in the same container after manufacturing, during storage, etc., and which can be stable for more than one month, for example, more than three months, more than six months, more than nine months, or more than twelve months, (substantially non-reacting or gelling) under conditions of 40-120°F (4-49°C) at a relative humidity of 0-95%.

[0052] As used herein, the term “organic filler” refers to carbon-containing or naturally derived materials that can be added to polymers and other materials, such as plastics, to act as fillers and / or to alter their properties.

[0053] As used herein, the term “organic solvent” refers to a carbon-based substance that can dissolve or disperse other substances.

[0054] As used herein, the term "oxazoline" refers to a molecule comprising a derivative of a five-membered heterocyclic organic moiety having the formula C3H5NO.

[0055] As used herein, the terms “pendant group” and “side group” refer to an atom or functional group bonded to the skeletal chain of a base molecule or polymer.

[0056] As used herein, the term “pigment” refers to a colored material, often an inorganic compound, that is insoluble in a solvent under ambient conditions.

[0057] As used herein, the term “polymer” includes homopolymers (formed from one monomer) and copolymers formed from two or more different monomers or containing two or more distinct repeating units. Furthermore, the term “polymer” includes prepolymers and oligomers. The term “polymer backbone” refers to atoms or monomer repeating units arranged in a long chain and does not include pendant groups. The term “polymer composition” refers to a compound or resin comprising at least one polymer and / or at least one other material.

[0058] As used herein, “polyol” refers to a compound having two or more hydroxyl groups, for example, two, three or four hydroxyl groups.

[0059] As used herein, the prefix "poly" refers to two or more. For non-limiting purposes, polyisocyanates refer to compounds containing two or more isocyanate groups, and polyols refer to compounds containing two or more hydroxyl groups.

[0060] As used herein, the term “powder composition” refers to a reactive composition containing less than 10% by weight of water or solvent, based on the weight of solid particles and the powder composition.

[0061] As used herein, the term “rheological modifier” refers to a material that alters the rheological properties of the fluid composition to which it is added.

[0062] As used herein, the term “ring unit” refers to the number of atoms in a ring structure. As non-limiting examples, cyclohexane, benzene, and pyridine have six ring units. In the case of pyridine, one ring unit is a heteroatom nitrogen.

[0063] As used herein, the term “sealant” refers to a material used to seal a substrate to make it airtight or watertight, preventing air or water from penetrating the substrate.

[0064] As used herein, the term “reactive composition” refers to a combination or mixture comprising a first compound containing a functional group and a second compound containing a functional group capable of chemically reacting with the functional group in the first compound.

[0065] As used herein, the term “solid” refers to the non-volatile (does not evaporate under ambient conditions) portion of a composition.

[0066] As used herein, the term “solvent resistance” refers to evaluating the degree of curing of a coating film by determining the film’s resistance to a specified solvent. As used herein, the solvent used is methyl ethyl ketone (MEK), and the method disclosed herein evaluates the film’s resistance or degree of curing as “MEK double lab.”

[0067] As used herein, the term “substrate” refers to the surface of an article to be coated, and may also refer to a coating layer previously placed on an article that may also be considered a substrate.

[0068] As used herein, the term “solvent” refers to a substance that can dissolve or disperse other substances under ambient conditions.

[0069] As used herein, the terms “terminal group” and “end group” refer to the portion or functional group attached to the end of a carbon chain (“terminal position”).

[0070] As used herein, the term “thermosetting” means a polymer or resin having functional groups that react with a crosslinking agent or functional groups in another polymer or molecule to form a network material, irreversibly converting a “flexible” polymer into a more rigid form. Often, thermosetting refers to a resin that is irreversibly “fixed” upon curing or crosslinking, where the polymer chains of the resin are joined together by covalent bonds. Once cured or crosslinked, thermosetting resins do not melt upon application of heat and are insoluble in solvents.

[0071] As used herein, the term “thermoplastic” refers to polymers and resins that are not bonded by covalent bonds and are thereby able to undergo a flow of liquid when heated and be soluble in certain solvents.

[0072] As used herein, the term “total neutralization” means all H from an acid such as a carboxylic acid. +This refers to complete neutralization, where an ion is neutralized by an equal amount of base.

[0073] As used herein, the terms “total solids,” “solids,” or “solids content” refer to the solids content as determined in accordance with ASTM D2369-20.

[0074] As used herein, the term “thioether group” refers to a functional group characterized by a sulfur atom bonded to two carbon atoms in any hybridization.

[0075] As used herein, the term "thiol" refers to a molecule containing one or more -SH groups. The term "polythiol" refers to a molecule that contains two or more thiol groups.

[0076] As used herein, “ultraviolet” and “ultraviolet light” refer to electromagnetic radiation capable of initiating photochemical reactions, such as, but not limited to, UVB and UVC radiation (180–315 nm) and near-UV radiation energies in the range of 320–380 nm (or 400 nm).

[0077] Where used herein, unless otherwise indicated, the term “viscosity” refers to a value determined at 23°C and ambient pressure, reflecting the resistance to fluid flow when subjected to shear stress and / or shear strain. Viscosity can be measured using a Brookfield viscometer (AMETEK, Inc.) with spindle number 7 at 50 rpm.

[0078] As used herein, the term "weight percent" refers to weight percent.

[0079] II. Reactive Compositions The reactive compositions disclosed herein Structure (I): [ka] A first compound comprising 1 to 12, for example, 1 to 10, or 1 to 6, or 1 to 5, or 1 to 4 carboxylic acid functional groups according to the formula, where R 1 However, it can be a C1-C6, for example, C1-C4, or a C1-C3 linear or branched alkyl group, where X is O, S, or NR 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, The present invention comprises a second compound containing a carboxylic acid functional group and a functional group reactive with the first compound.

[0080] While not limited to any single theory, if the acidic functional group is close to 1 to 6 carbon atoms, e.g., 1 to 4 or 1 to 3, of the urethane, urea, thiourea, or thiourethane group, the activity of the first compound containing the acidic functional group can be enhanced compared to the first compound without the urethane, urea, thiourea, or thiourethane group, or if the acidic functional group is separated from the urethane, urea, thiourea, or thiourethane group by more than 6 carbon atoms. While not limited to any single theory, the enhanced activity is thought to allow the compound containing the acidic functional group to react or cure at lower temperatures. Proximity is further thought to provide the benefit of carbonyls in the urethane, urea, thiourea, or thiourethane group interacting with the acidic functional group to further enhance the activity.

[0081] A. The first compound The first compound can be a molecule, a nonpolymer, or a polymer. Therefore, the first compound may contain a base molecule and / or a polymer backbone.

[0082] The first compound can be liquid under ambient conditions or have a melting point of at least about 30°C, such as at least about 50°C, or at least about 80°C, and a maximum of about 120°C, such as a maximum of about 110°C, or a maximum of about 100°C, or within any range using any two of the foregoing values as endpoints, such as 30°C to 120°C, or 30°C to 110°C, or 50°C to 100°C.

[0083] When the first compound is non-polymeric, it can have a molecular weight of less than 2,000 g / mol, such as less than 1,500 g / mol, or less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol, and the molecular weight is determined by summing the atomic weights of the individual atoms constituting the first compound.

[0084] When the first compound contains a base molecule, the base molecule can contain a molecular chain of 6 to 60, such as 6 to 50, or 6 to 40 linear, branched, cyclic, and / or aromatic carbon atoms, and optionally can contain heteroatoms such as O, S, or NR 5 wherein R 5 is H, methyl, ethyl, propyl, or isopropyl. The carboxylic acid functional group in the first compound can be a terminal group or pendant from the base molecule.

[0085] The base molecule can contain a cyclic moiety containing 5 to 14, such as 6 to 12 or 6 to 10 ring units, and optionally some of the ring units contain heteroatoms and the remaining ring units contain carbon.

[0086] The first compound can further contain a hydroxyl group, a thiol group, or any combination of the foregoing.

[0087] As shown above, the first compound may be a polymer containing one or more carboxylic acid groups. The acid value of the first compound may be determined using a Metrohm 798 MPT Titrino automatic titrator manufactured by Metrohm AG, according to ASTM D4662-15. The value may then be divided by the solid content to obtain the acid value on the solid. Thus, the polymer may have an acid value on the solid of 10 mg KOH to 250 mg KOH, for example, 20 mg KOH to 225 mg KOH, or 25 mg KOH to 200 mg KOH, according to ASTM D4662-15.

[0088] Carboxylic acid functional groups can be reaction products of isocyanates or polyisocyanates with compounds containing a carboxylic acid group and a hydroxyl, a carboxylic acid group and a thiol, and / or a carboxylic acid group and an amine.

[0089] The first compound is, but is not limited to, a reaction product of isophorone diisocyanate and mercaptopropionic acid, a reaction product of isophorone diisocyanate trimer and mercaptopropionic acid, a reaction product of hexamethylene diisocyanate trimer and mercaptopropionic acid, a reaction product of dicyclohexylmethane diisocyanate and mercaptopropionic acid, a reaction product of hexane diisocyanate and mercaptopropionic acid, tetramethylxylylene diisocyanate and Reaction products of mercaptopropionic acid, reaction products of isophorone diisocyanate and hydroxypropionic acid, reaction products of isophorone diisocyanate trimer and hydroxypropionic acid, reaction products of hexamethylene diisocyanate trimer and hydroxypropionic acid, reaction products of dicyclohexylmethane diisocyanate and hydroxypropionic acid, reaction products of hexane diisocyanate and hydroxypropionic acid, tetramethylxylylene diisocyanate and reaction products of hydroxypropionic acid, reaction products of isophorone diisocyanate and hydroxypivalic acid, reaction products of isophorone diisocyanate trimer and hydroxypivalic acid, reaction products of dicyclohexylmethane diisocyanate and hydroxypivalic acid, reaction products of hexane diisocyanate and hydroxypivalic acid, reaction products of tetramethylxylylene diisocyanate, reaction products of hydroxypivalic acid, cyclic carbonate and carboxylic acid-containing amines, reaction products of triphenylmethane triisocyanate and mercaptopropionic acid, reaction products of toluene-2,4,6-triyl triisocyanate and mercaptopropionic acid, reaction products of tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, reaction products of tetraisocyanate and mercaptopropionic acid, reaction products of triphenylmethane triisocyanate and hydroxypropionic acid, toluene-2,4,The reaction products of 6-triyltriisocyanate and hydroxypropionic acid, the reaction products of a tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, and hydroxypropionic acid, the reaction products of triphenylmethanetriisocyanate and hydroxypivalic acid, the reaction products of toluene-2,4,6-triyltriisocyanate and hydroxypivalic acid, and / or the reaction products of a tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, and hydroxypivalic acid may be included. If the first compound includes a polymer, it may include polymers containing urethane, urea, thiourea, or thiourethane repeating groups, (meth)acrylate repeating groups, ester repeating groups, amide repeating groups, and / or carbonate repeating groups.

[0090] If the first compound contains a polymer, the polymer may have a weight-average molecular weight of 2,000 g / mol to 50,000 g / mol, for example, 2,500 g / mol to 40,000 g / mol, or 3,000 g / mol to 30,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

[0091] The reactive compositions of the present disclosure may contain a first compound in an amount of 10% by weight or more, for example, 15% by weight or more, for example, 20% by weight or more, for example, 30% by weight or more, for example, 40% by weight or more, for example, 50% by weight or more, or 60% by weight or more up to 85% by weight, for example, up to 85% by weight, for example, up to 80% by weight or up to 70% by weight, or any range using any two of the aforementioned values ​​as endpoints, for example, 10% by weight or more to 85% by weight, or 15% by weight or more to 85% by weight, or 20% by weight or more to 80% by weight, or 30% by weight or more to 80% by weight, or 30% by weight or more to 70% by weight, or 40% by weight or more to 70% by weight, or 50% by weight or more to 80% by weight, or 60% by weight or more to 70% by weight, where the weight percent is based on the total resin solid.

[0092] B. Second compound The reactive compositions according to this disclosure comprise a second compound containing a carboxylic acid functional group in a first compound and a reactive functional group in the second compound. Examples of functional groups in the second compound include, but are not limited to, carbodiimide, epoxy, hydroxyl, thiol, primary amine, secondary amine, hydroxylamine, oxazoline, hydroxyalkylamide, hydroxyalkylurea, and / or aziridine functional groups.

[0093] The second compound can be a molecule, a nonpolymer, or a polymer. Therefore, the second compound may contain a base molecule and / or a polymer backbone.

[0094] The second compound may be liquid under ambient conditions, or have a melting point of at least about 30°C, e.g., at least about 50°C, or at least about 80°C, and may be at most about 120°C, e.g., at most about 110°C, or at most about 100°C, or within any range using any two of the aforementioned values ​​as endpoints, e.g., 30°C to 120°C, or 30°C to 110°C, or 50°C to 100°C.

[0095] If the second compound is a nonpolymer, it can have a molecular weight of less than 2,000 g / mol, for example, less than 1,500 g / mol, or less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol, and the molecular weight is determined by summing the atomic weights of the individual atoms that make up the second compound.

[0096] As a non-limiting example, the second compound includes resorcinol diglycidyl ether, 1,3,5-triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol, polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, trimethylpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether. Cydyl ether, polypropylene glycol diglycidyl ether, propyleneimine polyaziridine, trimethylolpropantris (2-methyl-1-aziridine propionate), ethyleneimine polyaziridine, trimethylolpropantris (2-methyl-1-aziridine propionate), tetramethylolmethanetris (β-aziridinyl propionate), trimethylolpropantris (β-aziridinyl propionate), 1,2-phenylene-bis-o Xazoline, 1,3-phenylene-bis-oxazoline, 1,4-phenylene-bis-oxazoline, 1,2-bis(oxazolinyl-4-methyl)benzene, 1,3-bis(oxazolinyl-4-methyl)benzene, 1,4-bis(oxazolinyl-4-methyl)benzene, 1,2-bis(oxazolinyl-5-ethyl)benzene, 1,3-bis(oxazolinyl-5-methyl)benzene, 1,3-bis(oxazolinyl-5-ethyl)benzene, 1,4-bis(oxazolinyl This may include (5-ethyl)benzene, 1,2,4-tris(oxazolinyl)benzene, 1,3,5-tris(oxazolinyl)benzene, and 1,2,4,5-tetrakis(oxazolinyl)benzene, acrylic oxazoline-functionalized reactive copolymers, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, polycarbodiimide, hydroxylalkylamides, for example, those available from Estron Chemical, Inc. under the trademark name PRIMID, (hydroxylalkyl)urea, and / or N,N,N'N'-tetrakis(β-hydroxylethyl)adipamide.

[0097] The second compound, though not limited to, has structure (II): [ka] An epoxy-functional compound comprising a structure according to the formula, wherein R 1 However, it can be a C1-C6, for example, C1-C4, or a C1-C3 linear or branched alkyl group, where X is O, S, or NR 2 It can be, R 2 However, H can be methyl, ethyl, propyl or isopropyl, and each R 3 and R 4 However, independently, it can be a base molecule and / or polymer backbone containing H, C1-C5 linear or branched alkyl groups, 6-60, for example, 6-50 or 6-40 linear, branched, cyclic, and / or aromatic carbon atom molecular chains, and optionally O, S, or NR 5 It can contain heteroatoms such as R 5 However, H can be methyl, ethyl, propyl, or isopropyl, and if necessary, one R 3 and R 4 However, it may contain epoxy-functional compounds that can form part of a base molecule containing a polymer backbone and / or 6 to 60, for example, 6 to 50, or 6 to 40 linear, branched, cyclic, and / or aromatic ring units, such as molecular chains of carbon atoms. 3 and R 4 However, independently, as needed, O, S, or NR 6 It can contain heteroatoms such as R 6 The group is H, methyl, ethyl, propyl, or isopropyl. The epoxy-functional compound can be a pendant from the terminal group and / or polymer backbone and / or base molecule.

[0098] As described above, and without being limited to any single theory, the activity of a first compound containing an acidic functional group can be enhanced when the acidic functional group is in proximity to a urethane, urea, thiourea, or thiourethane or urea group. Similarly, and without being limited to any single theory, the activity of a second compound containing an epoxy functional group can be enhanced when the epoxy functional group is in proximity to a urethane, urea, thiourea, or thiourethane group. Combined, the enhanced activity is thought to allow the first and second compounds to react or cure at lower temperatures.

[0099] The second compound may contain polymers comprising urethane, urea, thiourea, or thiourethane repeating groups, (meth)acrylate repeating groups, ester repeating groups, amide repeating groups, and / or carbonate repeating groups.

[0100] If the second compound contains a polymer, the polymer may have a weight-average molecular weight of more than 2,000 g / mol and up to 50,000 g / mol, for example, 2,500 g / mol to 40,000 g / mol, or 3,000 g / mol to 30,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

[0101] The reactive compositions of the present disclosure may also contain a second compound in an amount of 15% by weight or more, for example 20% by weight or more, for example 30% by weight or more, for example 40% by weight or more, for example 50% by weight or more, or 60% by weight or more to 90% by weight, for example up to 85% by weight, for example up to 80% by weight or up to 70% by weight, or any range using any two of the aforementioned values ​​as endpoints, for example 15% by weight or more to 90% by weight, or 15% by weight or more to 85% by weight, or 20% by weight or more to 80% by weight, or 30% by weight or more to 80% by weight, or 30% by weight or more to 70% by weight, or 40% by weight or more to 70% by weight, or 50% by weight or more to 80% by weight, or 60% by weight or more to 70% by weight, where the weight % is based on the total resin solid.

[0102] The reactive compositions of this disclosure may include mixtures in which the stoichiometric ratio of carboxylic acid groups in the first compound to reactive functional groups in the second compound is 1:10 to 10:1, for example, 1:7 to 7:1, or 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 1.0:1.3 to 1.3:1.0.

[0103] C.Catalyst The reactive compositions according to this disclosure may include a catalyst. The catalyst may include zinc, phosphine, amine, quaternary ammonium group, phosphonium, and / or quaternary phosphonium group.

[0104] If the reactive composition contains a catalyst, it can initiate the reaction between the functional groups of the first compound and the second compound, or allow the reaction to proceed at a modified rate. The catalyst is not consumed by the reaction.

[0105] If the catalyst contains an amine, the amine may be a tertiary amine such as an aromatic amine such as imidazole and / or pyridine, and / or an aliphatic amine such as diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and / or triethylamine.

[0106] The reactive compositions of this disclosure may be derived from a reaction mixture containing a catalyst in an amount of 0.05% by weight or more, for example, 0.1% by weight or more, or 0.25% by weight or more up to 2% by weight, for example, up to 1.5% by weight or up to 1% by weight, or any range using any two of the aforementioned values ​​as endpoints, for example, 0.05% by weight or more to 2% by weight, or 0.1% by weight or more to 1.5% by weight, or 0.25% by weight or more to 1% by weight, where the weight percentage is based on the weight of the reactive composition.

[0107] III. Reaction and / or curing The reactive compositions described herein react and / or cure at a faster rate and / or with less energy applied, for example, at a lower temperature, than compositions that do not contain compounds containing carboxylic acid functional groups following the structure (I) of the first compound, for example, if the acid functional group separates more than six carbon atoms from the urethane, urea, thiourea, or thiourethane group, or if the urethane, urea, thiourea, or thiourethane group is absent. When the reactive compositions described herein react and / or cure as described, they react more completely, i.e., more or all of the carboxylic acid functional groups following structure (I) react with the functional groups reactive with the carboxylic acid functional groups in the second compound, and as a non-limiting example, this can result in better solvent resistance, reflected in a higher MEK double-lab score, compared to compositions that do not contain compounds containing carboxylic acid functional groups following the structure (I) of the first compound.

[0108] A. Reactive composition As described above, the compositions described herein may include reaction products of the first and second compounds of the reactive composition. As shown, compared to a reactive composition that does not include the first compound, which contains a urethane, urea, thiourea, or a carboxylic acid functional group adjacent to a thiourethane group, as shown in structure (I) above, the first and second compounds react at a faster rate and / or at a lower temperature.

[0109] The reaction products of the first and second compounds of the reactive composition can be low molecular weight molecules, having a molecular weight of less than 2,000 g / mol, for example, less than 1,500 g / mol, or less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol.

[0110] If the reaction product of the first and second compounds of the reactive composition is a polymer, the polymer may have a weight-average molecular weight of over 2,000 to 50,000, for example, 2,500 to 40,000, or 3,000 to 30,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

[0111] B. Curable composition A reactive composition may be a curable composition. In a non-limiting example, if the reactive composition is a curable composition, the first compound may contain at least two carboxylic acid groups as shown in structure (I), and the second compound may contain at least two functional groups reactive with a carboxylic acid functional group. In a non-limiting example, if the reactive composition is a curable composition, the first compound may contain more than two carboxylic acid groups, and / or the second compound may contain more than two functional groups reactive with a carboxylic acid functional group. If at least one of the first and second compounds contains more than two carboxylic acid groups or groups reactive with a carboxylic acid functional group, the composition may be a thermosetting composition.

[0112] C. Physical form of reactive composition The reactive composition may be in the form of a liquid composition or a powder composition.

[0113] i. Powder composition When the reactive composition is in powder form, at ambient temperature, the reactive composition contains solid fine particles. The powder composition may be a curable composition as described above, and may contain a first compound and a second compound.

[0114] If the reactive composition is a powder composition, the powder composition contains 10% by weight or less of the solvent, for example, 5% by weight or less, or 2% by weight or less, and may be essentially solvent-free (less than 1% by weight), substantially solvent-free (less than 0.1% by weight), or completely solvent-free (undetectable by FTIR) based on the weight of the powder composition.

[0115] If the reactive composition is a powder composition, the powder composition may contain the oligomers and / or polymers described above. The oligomers and / or polymers may have a glass transition temperature of 20°C to 100°C, for example, 30°C to 90°C, or 40°C to 80°C, as determined by differential scanning calorimetry. If the glass transition temperature of the oligomers and / or polymers exceeds the aforementioned minimum value, the powder composition can be easily obtained by grinding and / or pulverizing it into a powder.

[0116] ii.Liquid composition If the reactive composition is in liquid form, it may contain solvents such as organic solvents and / or water. The liquid composition may be a curable composition as described above, comprising the first compound and the second compound.

[0117] If the reactive composition is a liquid composition, and is liquid under ambient conditions, it may not contain a solvent. In this case, the liquid composition is referred to as "solvent-free." The reactive composition may contain 30 to 80% by weight of solvent, for example, 30 to 70% by weight of solvent, or 40 to 60% by weight of solvent, based on the weight of the reactive composition, and the solvent may include water and / or organic solvents.

[0118] Suitable organic solvents that may be included in the solvent include, but are not limited to, esters, ketones, glycol ethers, alcohols, hydrocarbons, or mixtures thereof. Suitable ester solvents include alkyl acetates such as ethyl acetate, n-butyl acetate, n-hexyl acetate, and mixtures thereof. Suitable ketone solvents may include methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. Suitable hydrocarbon solvents may include toluene, xylene, aromatic hydrocarbons, and aliphatic hydrocarbons such as hexane, heptane, and nonane.

[0119] The liquid composition may contain an amount of organic solvent ranging from 0% by weight, for example, 10% by weight, or 20% by weight to a maximum of 60% by weight, for example, a maximum of 50% by weight, or a maximum of 40% by weight, or any range using any two of the aforementioned values ​​as endpoints, for example, 0% by weight to 60% by weight, or 10% by weight to 50% by weight, or 20% by weight to 40% by weight, where the weight percentage is based on the total weight of the liquid composition.

[0120] As a non-limiting example, if the liquid composition contains water, the liquid composition may contain neutralizing amines at levels of total neutralization of 40-120%, 40-80%, 40-90%, 60-100%, or 80-90%, based on the number of acidic groups in the reactive composition. Terms such as “neutralizing amine” refer to amines that can be used to neutralize at least some of compounds containing acidic functional groups, such as making the compound more water-soluble. A suitable neutralizing amine may be ammonia. A suitable neutralizing amine may be a secondary amine such as diethylamine. Furthermore, a suitable neutralizing amine may be a tertiary amine such as triethylamine, tributylamine, dimethylethanolamine, triethanolamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabisylco[5.4.0]undeca-7-ene, tripropylamine, and diisopropylethylamine. Neutralizing amines may include, but are not limited to, tertiary amines, ammonia, and combinations thereof.

[0121] The neutralizing amine can be present in an amount necessary to at least partially neutralize the acidic group in the first compound. 100% neutralization means that the molar ratio of the neutralizing amine to the acidic group is 1:1.

[0122] D. Additives The reactive compositions of this disclosure may further comprise one or more additives. Such additives may include solvents, surfactants, surface agents, catalysts, water, colorants including pigments and / or dyes, plasticizers, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic cosolvents, reactive diluents, leveling agents, defoamers, grinding vehicles, and other conventional auxiliaries.

[0123] E. End-use composition A composition containing a reactive composition or a reaction product derived therefrom may be in the form of a low molecular weight composition, a coating composition, an adhesive composition, or a sealant composition.

[0124] i. Low molecular weight composition Low molecular weight compositions can be useful in pharmaceutical and / or non-curable applications, as an example of a non-limiting model, and reactive compositions can be used as is or act as intermediates enabling the synthesis of a desired compound or target compound.

[0125] Low molecular weight compositions may include reaction products of the reactive compositions described herein. Low molecular weight reaction products may have a molecular weight of less than 2,000 g / mol, for example, less than 1,500 g / mol, or less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol.

[0126] Low molecular weight compositions may contain chiral centers, and compositions may contain stereoisomers, diastereomers, and enantiomers, and / or racemic mixtures.

[0127] ii. Adhesives As described above, this disclosure provides a reactive composition suitable for use as an adhesive. When used as an adhesive, the reactive composition may be in the form of a 1K ("one-component"), 2K ("two-component"), or multi-component adhesive composition that can be used to bond two substrate materials together for a wide variety of potential applications, where the bond between the substrate materials provides specific mechanical properties with respect to elongation, tensile strength, lap shear strength, T peel strength, coefficient, or impact peel strength. If the adhesive is a 1K composition, the first compound and / or the second compound may be blocked. The adhesive may be applied to either one or both of the materials being bonded. The bond thickness may be controlled by aligning the pieces and adding pressure and spacers. The adhesive may be a curable composition as described above. For 2K and multi-component adhesives, compounds containing acidic groups, as well as compounds containing acidic and reactive groups such as carbodiimide, epoxy, hydroxyl, thiol, primary amines, secondary amines, hydroxylamines, oxazolines, hydroxyalkylamides, hydroxyalkylureas, and / or aziridine functional groups, are separate components, and curing begins when the components are mixed together at ambient temperature or slightly higher. In contrast to 1K adhesives, adhesives can be cured using an external source such as an oven (or other heat means) or by using chemical radiation (such as UV light).

[0128] Suitable substrate materials that can be bonded by this adhesive composition include, but are not limited to, materials such as metals or metal alloys, natural materials such as wood, polymer materials such as hard plastics, or composite materials.

[0129] iii. Sealant The reactive and curable compositions of this disclosure can be advantageously used as sealants, particularly as sealants where low temperature (below 20°C) flexibility and resistance to fuel are desirable attributes.

[0130] The reactive and curable compositions of this disclosure can be prepared by combining a first component comprising a compound containing an acidic group and a second component comprising a compound containing a group reactive with an acidic group, such as a compound containing a carbodiimide, epoxy, hydroxyl, thiol, primary amine, secondary amine, hydroxylamine, oxazoline, hydroxyalkylamide, hydroxyalkylurea, and / or a compound containing an aziridine functional group. If the sealant is a 1K composition, the first compound and / or the second compound can be blocked. The first and second components can be combined in a desired ratio, for example, using an instrument mixer equipped with a dynamic mixing head. Pressure from the instrument mixer can force the first and second components through the dynamic mixing head and extrusion die. The first and second components can be combined immediately before application to the surface to be sealed.

[0131] The reactive and curable compositions of this disclosure can be useful as sealants for sealing welded joints of metal automotive panels and / or metal surfaces such as Mil-C and / or AMS surfaces, including stainless steel, aluminum, and / or Alkalad surfaces.

[0132] The reactive and curable compositions of this disclosure can be applied to a surface by any means known to those skilled in the art, and when suitable for a particular application, including extrusion, pressing, grouting, caulking, spreading, etc.

[0133] The reactive and curable compositions of this disclosure can be cured at ambient temperature according to recommended procedures, as can be determined by those skilled in the art as non-limiting examples. The reactive and curable compositions can be reacted at the lowest temperature below 0°C, for example, -10°C or -20°C.

[0134] iv. Coating composition The reactive compositions of this disclosure may be applied as coating compositions to articles or substrates using spray coating, roller coating, coil coating, dip coating, precision coating, or spin coating techniques. The reactive compositions may be deposited on at least a portion of the surface of an article and cured to form a cured layer.

[0135] The coating composition can be used in methods of coating a substrate, which include applying the reactive composition to at least a portion of the substrate using spray coating, roller coating, coil coating, dip coating, precision coating, or spin coating techniques, and curing the reactive composition to form a cured layer.

[0136] The coating composition may be in the form of a 1K ("one-component"), 2K ("two-component"), or multi-component coating composition. If the coating composition is a 1K composition, the first compound and / or the second compound may be blocked.

[0137] The coating composition may contain one or more layers of a multilayer coating. In a non-limiting example, the coating composition may be a primer coat, a base coat or color coat layer, and / or a clear coat layer. In a non-limiting example, the coating composition may be a primer coat and / or a top coat.

[0138] After coating the substrate, and before curing the reactive curable composition, it can be flashed for 5 to 60 minutes, for example, 5 to 60 minutes, for example, 5 to 30 minutes, at a temperature of 10°C to 80°C, for example, 20°C to 60°C, for example, 20°C to 40°C.

[0139] The curable compositions of this disclosure may be curable at temperatures ranging from 0°C to, for example, 20°C, or 40°C, or 60°C, or 80°C, or 100°C to a maximum of 120°C, for example, a maximum of 140°C, or a maximum of 160°C, or a maximum of 215°C, or a maximum of 225°C, or a maximum of 240°C, or a maximum of 260°C, or any range using any two of the aforementioned values ​​as endpoints, for example, 0°C to 260°C, or 20°C to 240°C, or 40°C to 225°C, or 60°C to 225°C, or 80°C to 215°C, or 100°C to 215°C. The curable compositions may be cured for 5 seconds to 48 hours, for example, 5 seconds to 24 hours, or 10 seconds to 12 hours, or 1 minute to 12 hours, or 1.5 minutes to 12 hours, or 1.75 minutes to 12 hours. If necessary, before curing, the curable composition to be applied may be flashed for 5 to 60 minutes, for example, 5 to 30 minutes, at a temperature of 10°C to 80°C, for example, 20°C to 60°C, for example, 20°C to 40°C, for example, ambient temperature (20°C) to 40°C.

[0140] As will be understood by those skilled in the art, the time and temperature used for curing will be adjusted according to the needs of the particular application. For example, this application may include coil coatings that can be cured at high temperatures for a short time, in a non-limiting example, 180-220°C for 5-20 seconds. Another non-limiting example may be automotive applications in which the curable composition of this disclosure can be cured at a temperature of 80-140°C for 10 minutes to 1 hour. In further examples such as automotive refinishing or industrial applications, the curable composition of this disclosure may be cured at a temperature of 0-80°C for 5 minutes to 48 hours.

[0141] The coating composition can be a curable composition formed as described above, and can exhibit increased resistance to solvents compared to a coating derived from a composition that does not contain the first compound according to structure (I) and, optionally, the second compound according to structure (II).

[0142] To test the resistance of a coating composition, a substrate coated with the coating composition may be subjected to a solvent resistance test as described below.

[0143] Solvent resistance testing can be performed by placing the test panel on a flat table or other suitable flat, hard surface. Two sterile gauze pads can be secured to the end of a 1-pound ball peen hammer. The gauze can be secured so that there are four layers of gauze on the wrinkle-free end of the hammer, held snugly in place with elastic bands.

[0144] The gauze is saturated with a suitable solvent, such as methyl ethyl ketone (MEK), for the substrate being tested. The gauze is resaturated after every 25 double rubs.

[0145] The substrate coated with the curable composition is immediately rubbed with saturated gauze across the test area using a 2-4 inch back-and-forth stroke. The weight of the hammer controls the downward pressure.

[0146] The forward and backward strokes may be continued, and one “double love” is counted for each completed forward and backward movement until the bare substrate is exposed in the center of the strip where the double love is performed, or until 100 double loves are achieved.

[0147] The number of "double labs" is recorded as the test result (MEK double lab). The gauze must be removed and replaced with a new piece of gauze between each sample tested.

[0148] The coating compositions according to this disclosure (coatings derived from compositions comprising a first compound according to structure (I) and optionally a second compound according to structure (II)) can exhibit increased solvent resistance, as demonstrated by the MEK double lab, compared to coatings derived from compositions that do not contain the first compound according to structure (I) or the second compound according to structure (II).

[0149] v. Three-dimensional printing The reactive compositions described herein can be used to produce articles by ambient reactive extrusion (three-dimensional printing). The articles can be produced using the first and second compounds described above.

[0150] The reactive and / or curable compositions described above may be suitable for use with ambient reactive extrusion (ARE) in accordance with this disclosure. This broadly includes thermosetting polymers (sometimes referred to as thermosetting materials), thermoplastic polymers, or combinations thereof. Co-reactive components, selected by those skilled in the art to yield a desired curable composition for formulating articles, include a first compound and a second compound.

[0151] Articles according to this disclosure are manufactured additively by extruding a curable composition onto a surface, for example, a construction platform. The reactive composition is at least partially reacted at the time of extrusion and may then fully react and cure to form a layer of curable composition. Consecutive layers of the same and / or different curable compositions may be deposited to form additional layers of material. The combination of layers forms an article. The curable composition may at least partially react immediately before extrusion when a first compound and a second compound are brought together in a mixed volume, for example. Alternatively, the two co-reactive compounds may be pre-mixed before extrusion and the composition may be frozen after mixing to stop the reaction between the co-reactive compounds.

[0152] It may be desirable to select the chemical properties of each layer of the deposited curable composition so that covalent bonds are formed between consecutive layers. Different parts of an article can be printed from different curable compositions (e.g., a first curable composition printed to form a first part of an object, such as a base or internal structure, and a second curable composition printed to form a second part of the object). Depending on the chemical reactivity between the different curable compositions, covalent bonds may also be formed between the different materials.

[0153] Articles may be printed to have rigid parts (that cannot be bent without breaking) and flexible parts (that do not break when first bent), rigid parts and bubbly parts (the curable composition contains voids), tactile parts (textured) and rigid and / or flexible parts, two or more parts with different densities, one or more conductive parts, one or more thermal / electrically conductive parts (that allow heat or electricity to pass through), two or more different colors, two or more different rheological profiles, two or more different materials with different affinities to water and / or solvents, etc. Articles may also be printed so that the curable composition is deposited on an existing article (e.g., other thermosetting materials and / or thermoplastics, metals, wood, composites, ceramics, etc.).

[0154] Peripheral manufacturing as described herein can result in objects with higher strength compared to other extruded or printed parts resulting from covalent bonding between printed layers, particularly along the Z (e.g., vertical) axis. Strong intra- and inter-layer covalent bonding results in stronger parts as well as more uniform part shapes, i.e., fewer print lines and / or part differences. Thus, this disclosure provides the ability to form objects having multiple substrates and / or parts containing different compositions in a single process.

[0155] Articles can form at least part of structures such as vehicles, manufactured goods, consumer electronic devices, consumer electrical appliances, pavement, road markings, or components of modular housings.

[0156] The reactive composition can be applied as a multilayer, with the first reactive composition being applied as the first layer, and the second reactive composition being applied to the surface of the first reactive composition to form the second layer. The first reactive composition and / or the second reactive composition comprises the first compound and the second compound.

[0157] The viscosities of the first and second reactive compositions can range from 1 cps to 1,000,000 cps, e.g., 250 cps to 500,000 cps, 300 cps to 100,000 cps, or 500 to 50,000 cps, determined at 23°C using a Brookfield viscometer (AMETEK, Inc.) with spindle number 7 at 50 rpm.

[0158] manner Appearance 1. Structure (I): [ka] A first compound comprising 1 to 12 carboxylic acid functional groups according to the formula, wherein R 1 However, the alkyl group is C1-C6, for example, C1-C4, or C1-C3 linear or branched alkyl, and X is O, S, or NR. 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, A reactive composition comprising a second compound having a functional group that is reactive with the carboxylic acid functional group in the first compound.

[0159] Appearance 2. Structure (I): [ka] A first compound comprising 1 to 10 carboxylic acid functional groups according to the formula, wherein R 1 However, the alkyl group is C1-C6, for example, C1-C4, or C1-C3 linear or branched alkyl, and X is O, S, or NR. 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, A reactive composition comprising a second compound having a functional group that is reactive with the carboxylic acid functional group in the first compound.

[0160] Appearance 3. Structure (I): [ka] A first compound comprising 1 to 6 carboxylic acid functional groups according to the formula, where R 1 However, the alkyl group is C1-C6, for example, C1-C4, or C1-C3 linear or branched alkyl, and X is O, S, or NR. 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, A reactive composition comprising a second compound having a functional group that is reactive with the carboxylic acid functional group in the first compound.

[0161] Appearance 4. Structure (I): [ka] A first compound comprising 1 to 5 carboxylic acid functional groups according to the formula, wherein R 1 However, the alkyl group is C1-C6, for example, C1-C4, or C1-C3 linear or branched alkyl, and X is O, S, or NR. 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, A reactive composition comprising a second compound having a functional group that is reactive with the carboxylic acid functional group in the first compound.

[0162] Appearance 5. Structure (I): [ka] A first compound comprising 1 to 4 carboxylic acid functional groups according to the formula, where R 1 However, the alkyl group is C1-C6, for example, C1-C4, or C1-C3 linear or branched alkyl, and X is O, S, or NR. 2 And R 2 However, the first compound is H, methyl, ethyl, propyl, or isopropyl, A reactive composition comprising a second compound having a functional group that is reactive with the carboxylic acid functional group in the first compound.

[0163] Appearance 6.R 1 The reactive composition according to any preceding embodiment, wherein the alkyl group is C1-C4, or a C1-C3 linear or branched alkyl group.

[0164] Embodiment 7. The first compound comprises a polymer backbone and / or a base molecule containing a molecular chain of 6 to 60, for example, 6 to 50 or 6 to 40 linear, branched, cyclic and / or aromatic carbon atoms, and optionally O, S or NR 5 It can contain heteroatoms including R 5 The reactive composition according to any preceding embodiment, wherein the carboxylic acid functional group is H, methyl, ethyl, propyl, or isopropyl, and the carboxylic acid functional group is included as a terminal group and / or a pendant group from the polymer backbone and / or the base molecule.

[0165] Embodiment 8. The reactive composition according to Embodiment 7, wherein the base molecule comprises a cyclic portion containing 5 to 14 ring units, and optionally some of the ring units contain heteroatoms and the remaining ring units contain carbon.

[0166] Embodiment 9. The reactive composition according to Embodiment 8, wherein the base molecule comprises a cyclic portion containing 6 to 12 or 6 to 10 ring units.

[0167] Embodiment 10. A reactive composition according to any preceding embodiment, wherein the first compound comprises a polymer containing a carboxylic acid group and has an acid value of 10 mg KOH to 250 mg KOH on a solid surface according to ASTM D4662-15.

[0168] Embodiment 11. The reactive composition according to any preceding embodiment, wherein the first compound comprises a polymer containing a carboxylic acid group and has an acid value of 20 mg KOH to 225 mg KOH, for example 25 mg KOH to 200 mg KOH, on a solid basis according to ASTM D4662-15.

[0169] Embodiment 12. The reactive composition according to any preceding embodiment, wherein the carboxylic acid functional group is a reaction product of an isocyanate and a compound comprising a carboxylic acid group and a hydroxyl, a carboxylic acid group and a thiol, and / or a carboxylic acid group and an amine.

[0170] Embodiment 13. The first compound is a reaction product of isophorone diisocyanate and mercaptopropionic acid, a reaction product of isophorone diisocyanate trimer and mercaptopropionic acid, a reaction product of hexamethylene diisocyanate trimer and mercaptopropionic acid, a reaction product of dicyclohexylmethane diisocyanate and mercaptopropionic acid, a reaction product of hexane diisocyanate and mercaptopropionic acid, a reaction product of tetramethylxylylene diisocyanate and Reaction products of mercaptopropionic acid, reaction products of isophorone diisocyanate and hydroxypropionic acid, reaction products of isophorone diisocyanate trimer and hydroxypropionic acid, reaction products of hexamethylene diisocyanate trimer and hydroxypropionic acid, reaction products of dicyclohexylmethane diisocyanate and hydroxypropionic acid, reaction products of hexane diisocyanate and hydroxypropionic acid, tetramethylxylylene diisocyanate Reaction products of tetraisocyanate and hydroxypropionic acid, reaction products of isophorone diisocyanate and hydroxypival acid, reaction products of isophorone diisocyanate trimer and hydroxypival acid, reaction products of dicyclohexylmethane diisocyanate and hydroxypival acid, reaction products of hexane diisocyanate and hydroxypival acid, reaction products of tetramethylxylylene diisocyanate, reaction products of hydroxypival acid, cyclic carbonate and carboxylic acid-containing amines, reaction products of triphenylmethane triisocyanate and mercaptopropionic acid, reaction products of toluene-2,4,6-triyl triisocyanate and mercaptopropionic acid, reaction products of tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, reaction products of tetraisocyanate and mercaptopropionic acid, reaction products of triphenylmethane triisocyanate and hydroxypropionic acid, toluene-2,4A reactive composition according to any preceding embodiment, comprising: a reaction product of 6-triyltriisocyanate and hydroxypropionic acid; a reaction product of a tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, and hydroxypropionic acid; a reaction product of triphenylmethanetriisocyanate and hydroxypivalic acid; a reaction product of toluene-2,4,6-triyltriisocyanate and hydroxypivalic acid; and / or a reaction product of a tetraisocyanate according to the structure C(CH2O(CH2CH2O)nCH2CH2NCO)4, where n is 1 to 20, and hydroxypivalic acid.

[0171] Embodiment 14. A reactive composition according to any preceding embodiment, wherein the first compound comprises a polymer containing a urethane repeating group, a urea repeating group, a thiourea repeating group, a thiourethane repeating group, a (meth)acrylate repeating group, an ester repeating group, an amide repeating group, and / or a carbonate repeating group.

[0172] Embodiment 15. A reactive composition according to any preceding embodiment, wherein the first compound is present in an amount of 10% to 85% by weight, and the weight percentage is based on total resin solids.

[0173] Embodiment 16. A reactive composition according to any preceding embodiment, wherein the first compound is present in an amount of 15% to 85% by weight, for example, 20% to 80% by weight, or 30% to 80% by weight, or 30% to 70% by weight, or 40% to 70% by weight, or 50% to 80% by weight, or 60% to 70% by weight, and the weight % is based on the total resin solid.

[0174] Embodiment 17. The reactive composition according to any preceding embodiment, wherein the second compound comprises a carbodiimide, epoxy, hydroxyl, thiol, primary amine, secondary amine, hydroxylamine, oxazoline, hydroxyalkylamide, hydroxyalkylurea, and / or aziridine functional group.

[0175] Embodiment 18. The second compound is resorcinol diglycidyl ether, 1,3,5-triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol, polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, trimethylpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polypropylene glycol Ludiglycidyl ether, propyleneimine polyaziridines, trimethylolpropantris (2-methyl-1-aziridine propionate), ethyleneimine polyaziridines, trimethylolpropantris (2-methyl-1-aziridine propionate), tetramethylolmethanetris (β-aziridinyl propionate), trimethylolpropantris (β-aziridinyl propionate), 1,2-phenylene-bis-oxazoline, 1,3-phenylene-bis-oxazoline, 1,4-phenylene- Bis-oxazoline, 1,2-bis(oxazolinyl-4-methyl)benzene, 1,3-bis(oxazolinyl-4-methyl)benzene, 1,4-bis(oxazolinyl-4-methyl)benzene, 1,2-bis(oxazolinyl-5-ethyl)benzene, 1,3-bis(oxazolinyl-5-methyl)benzene, 1,3-bis(oxazolinyl-5-ethyl)benzene, 1,4-bis(oxazolinyl-5-ethyl)benzene, 1,2,4-tris(oxazolinyl)benzene, 1,3,5-tris(oxazolinyl A reactive composition according to any prior embodiment, comprising benzene, and 1,2,4,5-tetrakis(oxazolinyl)benzene, acrylic oxazoline-functionalized reactive copolymer, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, polycarbodiimide, hydroxylalkylamide, (hydroxylalkyl)urea and / or N,N,N',N'-tetrakis(β-hydroxylethyl)adipamide.

[0176] Embodiment 19. The second compound has structure (II): [ka] The compound comprises an epoxy-functional compound having a structure according to the formula, where R 1 However, it is a C1-C6 linear or branched alkyl group, and X is O, S, or NR 2 And R 2 However, it is H, methyl, ethyl, propyl, or isopropyl. Each R 3 and R 4 However, independently, it can be a base molecule containing H, C1-C5 linear or branched alkyl groups, 6-60 linear, branched, cyclic and / or aromatic carbon atom molecular chains, and / or polymer backbone, and optionally O, S, or NR 5 It can contain heteroatoms including R 5 However, H is methyl, ethyl, propyl, or isopropyl, and if necessary, one R 3 and R 4 However, it can form part of a base molecule that includes a polymer backbone and / or molecular chains of 6 to 60 linear, branched, cyclic, and / or aromatic carbon atoms. Each R 3 and R 4 However, independently, as needed, O, S, or NR 6 It can contain heteroatoms including R 6 is H, methyl, ethyl, propyl, or isopropyl, The reactive composition according to any preceding embodiment, wherein the epoxy-functional compound is included as terminal groups and / or pendant groups from the polymer backbone and / or the base molecule.

[0177] Appearance 20.R 1 The reactive composition according to embodiment 19, wherein the C1-C4 group is, for example, a C1-C3 linear or branched alkyl group.

[0178] Appearance 21. Each R 3 and R 4The reactive composition according to embodiment 19, wherein the base molecule comprises 6 to 50, for example, 6 to 40 linear, branched, cyclic, and / or aromatic carbon atom molecular chains.

[0179] Embodiment 22. The one R as needed 3 and R 4 The reactive composition according to embodiment 19, wherein a base molecule is formed comprising 6 to 50, for example, 6 to 40, linear, branched, cyclic, and / or aromatic carbon atom molecular chains.

[0180] Embodiment 23. The reactive composition according to any preceding embodiment, wherein the second compound comprises a polymer containing a urethane repeating group, a urea repeating group, a thiourea repeating group, a thiourethane repeating group, a (meth)acrylate repeating group, an ester repeating group, an amide repeating group, and / or a carbonate repeating group.

[0181] Embodiment 24. A reactive composition according to any preceding embodiment, wherein the second compound is present in an amount of 15% to 90% by weight, and the weight percentage is based on the total resin solid.

[0182] Embodiment 25. A reactive composition according to any preceding embodiment, wherein the second compound is present in an amount of 15% to 85% by weight, for example, 20% to 80% by weight, or 30% to 80% by weight, or 30% to 70% by weight, or 40% to 70% by weight, or 50% to 80% by weight, or 60% to 70% by weight, and the weight % is based on the total resin solid.

[0183] Embodiment 26. A reactive composition according to any prior embodiment, further comprising a catalyst.

[0184] Embodiment 27. The reactive composition according to Embodiment 26, wherein the catalyst comprises zinc, phosphine, amine, quaternary ammonium group, phosphonium, and / or quaternary phosphonium group.

[0185] Embodiment 28. The reactive composition according to Embodiment 27, wherein the amine is a tertiary amine such as imidazole and / or an aromatic amine such as pyridine, and / or an aliphatic amine such as diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,4-diazabicyclo[2.2.2]octane and / or triethylamine.

[0186] A reactive composition according to any one of Aspects 18 to 20, wherein it comprises a catalyst in an amount of % to 2% by weight, the % by weight being based on the weight of the reactive composition.

[0187] A reactive composition according to any one of embodiments 18 to 20, comprising a catalyst in an amount of 0.1% to 1.5% by weight, such as embodiment 30.0.25% to 1% by weight, wherein the weight percentage is based on the weight of the reactive composition.

[0188] Embodiment 31. The reactive composition according to any preceding embodiment, wherein the first compound comprises at least two carboxylic acid groups, and the second compound comprises at least two functional groups reactive with the carboxylic acid functional groups.

[0189] Embodiment 32. The reactive composition according to any prior embodiment, wherein the reactive composition is a curable composition.

[0190] Embodiment 33. The reactive composition according to any preceding embodiment, wherein the reactive composition is a curable composition, the first compound comprises two or more carboxylic acid groups, and / or the second compound comprises two or more functional groups that are reactive with the carboxylic acid functional groups.

[0191] Embodiment 34. A reactive composition according to any prior embodiment, in the form of a powder composition.

[0192] Embodiment 35. A reactive composition according to any preceding embodiment, in the form of a liquid composition.

[0193] Embodiment 36. The reactive composition according to any preceding embodiment, in the form of a one-component composition or a two-component composition, or any other multi-component composition, wherein the first compound is contained in one component and the second compound is contained in a different component.

[0194] Embodiment 37. The reactive composition according to Embodiment 36, wherein the first component and / or the second component are blocked.

[0195] Embodiment 38. The reactive composition according to any one of Embodiments 35 to 37, wherein the liquid composition is liquid under ambient conditions and is solvent-free, or the liquid composition contains 20 to 80% by weight of a solvent, for example, 30 to 70% by weight of a solvent, or 40 to 60% by weight of a solvent, based on the weight of the reactive composition, and the solvent contains water and / or an organic solvent.

[0196] Embodiment 39. The reactive composition according to any one of Embodiments 35 to 38, wherein the liquid composition comprises 30 to 70% by weight of a solvent, for example, 40 to 60% by weight of the reactive composition, and the solvent comprises water and / or an organic solvent.

[0197] Embodiment 40. The reactive composition according to any one of embodiments 35 to 39, further comprising a neutralizing amine at a level of total neutralization of 40 to 120% based on the number of acidic groups in the reactive composition.

[0198] Embodiment 41. The reactive composition according to any one of Embodiments 35 to 40, further comprising a neutralizing amine at a level of 40 to 80%, for example, 40 to 90% or 60 to 100%, or 80 to 90%, based on the number of acidic groups in the reactive composition.

[0199] Embodiment 42. The reactive composition according to either Embodiment 40 or Embodiment 41, wherein the neutralizing amine comprises a tertiary amine, ammonia, and combinations thereof.

[0200] Embodiment 43. A reactive composition according to any preceding embodiment, in the form of a coating composition, adhesive composition, or sealant composition.

[0201] Embodiment 44. The reactive composition according to any preceding embodiment, wherein the stoichiometric ratio of the carboxylic acid group in the first compound to the reactive functional group in the second compound is 1:10 to 10:1.

[0202] Embodiment 45. A reactive composition according to any preceding embodiment, wherein the stoichiometric ratio of the carboxylic acid group in the first compound to the reactive functional group in the second compound is 1:7 to 7:1, for example, 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 1.0:1.3 to 1.3:1.0.

[0203] Embodiment 46. A composition comprising a reaction product of a reactive composition described in any prior embodiment.

[0204] Embodiment 47. The composition according to Embodiment 46, wherein the reaction product has a molecular weight of less than 2,000 g / mol.

[0205] Embodiment 48. The composition according to Embodiment 46, wherein the reaction product has a molecular weight of less than 1,500 g / mol, for example, less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol.

[0206] Embodiment 49. The composition according to any one of Embodiments 46 to 48, wherein the reaction product comprises a chiral center, a stereoisomer, an enantiomer, and / or a diastereomer.

[0207] Embodiment 50. The composition according to any one of Embodiments 46 to 49, wherein the composition is a racemic mixture.

[0208] Embodiment 51. The composition according to Embodiment 46, wherein the reaction product is a polymer having a weight-average molecular weight of 2,000 to 50,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

[0209] Embodiment 52. The composition according to Embodiment 46, wherein the reaction product is a polymer having a weight-average molecular weight of 2,500 to 40,000, for example, 3,000 to 30,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

[0210] Embodiment 53. A method for coating a substrate, comprising: applying one of the reactive compositions of Embodiments 1 to 45 to at least a portion of the substrate using spray coating, roller coating, coil coating, dip coating, precision coating, or spin coating techniques; and curing the reactive composition to form a cured layer.

[0211] Embodiment 54. The method according to Embodiment 53, wherein the cured layer is part of a multilayer coating, and the cured layer includes a primer coat, a base coat or color coat layer, and / or a clear coat layer.

[0212] Embodiment 55. The method according to either Embodiment 53 or 54, wherein the reactive composition is reacted at a temperature of 0°C to 260°C for 5 seconds to 168 hours.

[0213] Embodiment 56. The method according to either Embodiment 53 or 54, wherein the reactive composition is reacted at a temperature of 20°C to 240°C, for example, 40°C to 225°C, or 60°C to 225°C, or 80°C to 215°C, or 100°C to 215°C, for 5 seconds to 48 hours, for example, 5 minutes to 24 hours, or 10 minutes to 12 hours, or 10 minutes to 12 hours, or 20 minutes to 12 hours, or 15 minutes to 12 hours.

[0214] Embodiment 57. The method according to any one of Embodiments 53 to 56, wherein the reactive composition is flashed at a temperature of 10°C to 80°C for 5 to 60 minutes before being reacted.

[0215] Embodiment 58. The method according to any one of Embodiments 53 to 56, wherein the reactive composition is flashed at a temperature of 20°C to 60°C, for example, 20°C to 40°C, for 5 to 30 minutes before being reacted.

[0216] Embodiment 59. The method according to any one of Embodiments 53 to 58, wherein the reactive composition reacts when less energy is applied, for example, at a lower temperature, than a composition that does not contain a compound having a carboxylic acid functional group according to structure (I).

[0217] Embodiment 60. The method according to any one of Embodiments 53 to 59, wherein the reactive composition reacts faster at the same temperature than a composition that does not contain the compound comprising the carboxylic acid functional group according to structure (I).

[0218] Embodiment 61. The method according to any one of Embodiments 53 to 60, wherein the reactive composition comprises a first compound having structure (I) and a second compound having structure (II), and does not contain a compound having the carboxylic acid functional group according to structure (I), or contains a compound having the carboxylic acid functional group according to structure (I), but does not contain a second compound having structure (II), and reacts when less energy is applied, for example, at a lower temperature, than a composition.

[0219] Embodiment 62. The method according to any one of Embodiments 53 to 61, wherein the reactive composition comprises a first compound containing the carboxylic acid functional group according to structure (I) and a second compound containing structure (II), and reacts faster at the same temperature than a composition that does not contain the compound containing the carboxylic acid functional group according to structure (I), or a composition that contains the carboxylic acid functional group according to structure (I) but does not contain the second compound containing structure (II).

[0220] Embodiment 63. A method for producing the composition according to any one of Embodiments 53 to 61, comprising reacting the reactive composition at a temperature of 0°C to 260°C for 5 seconds to 48 hours to provide a reaction product.

[0221] Embodiment 64. A method for producing the composition according to any one of Embodiments 53 to 61, comprising reacting the reactive composition at a temperature of 20°C to 240°C, for example, 40°C to 225°C, or 60°C to 225°C, or 80°C to 215°C, or 100°C to 215°C for 5 minutes to 24 hours, for example, 10 minutes to 12 hours, or 10 minutes to 12 hours, or 20 minutes to 12 hours, or 15 minutes to 12 hours, to provide a reaction product.

[0222] Embodiment 65. An article comprising a reactive composition according to any one of Embodiments 1 to 45 deposited on at least a portion of the surface of the article.

[0223] Embodiment 66. A manufactured article produced by ambient reactive extrusion using a reactive composition according to any one of Embodiments 1 to 45.

[0224] Embodiment 67. The article according to Embodiment 66, wherein the article forms at least part of a structure such as a vehicle, a manufactured article, a consumer electronic device, a consumer electrical appliance, pavement, road marking, or a component of a modular housing.

[0225] Embodiment 68. The reactive composition is coated as a multilayer, The first reactive composition is applied as the first layer. The article according to either embodiment 66 or 67, wherein a second reactive composition is applied to the surface of the first reactive composition to constitute a second layer.

[0226] Embodiment 69. An article according to any one of Embodiments 66 to 68, wherein the viscosity of the first and second reactive compositions is 1 cps to 1,000,000 cps, determined at 23°C.

[0227] Embodiment 70. An article according to any one of Embodiments 66 to 68, wherein the viscosity of the first and second reactive compositions is 250 cps to 500,000 cps, for example, 300 cps to 100,000 cps, or 500 to 50,000 cps, as determined at 23°C.

[0228] Embodiment 71. A method for improving the reactivity of a carboxylic acid functional group with a reactive group, wherein the method is A first compound according to structure (I) of embodiment 1, This includes reacting the first compound with a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound, The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group separates more than six carbon atoms from the urethane, urea, thiourea, or thiourethane group, or the urethane, urea, thiourea, or thiourethane group is not present.

[0229] Embodiment 72. A method for improving the reactivity of a carboxylic acid functional group with a reactive group, wherein the method is A first compound according to structure (I) of embodiment 2, This includes reacting the first compound with a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound, The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group separates more than six carbon atoms from the urethane, urea, thiourea, or thiourethane group, or the urethane, urea, thiourea, or thiourethane group is not present.

[0230] Embodiment 73. A method for improving the reactivity of a carboxylic acid functional group with a reactive group, wherein the method is A first compound according to structure (I) of embodiment 3, This includes reacting the first compound with a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound, The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group separates more than six carbon atoms from the urethane, urea, thiourea, or thiourethane group, or the urethane, urea, thiourea, or thiourethane group is not present.

[0231] Embodiment 74. A method for improving the reactivity of a carboxylic acid functional group with a reactive group, wherein the method is A first compound according to structure (I) of embodiment 4, This includes reacting the first compound with a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound, The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group separates more than six carbon atoms from the urethane, urea, thiourea, or thiourethane group, or the urethane, urea, thiourea, or thiourethane group is not present.

[0232] Embodiment 75. A method for improving the reactivity of a carboxylic acid functional group with a reactive group, wherein the method is A first compound according to structure (I) of embodiment 5, This includes reacting the first compound with a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound, The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), and the acid functional group separates more than 6 carbon atoms from the urethane, urea, thiourea, or thiourethane group, or does not contain the urethane, urea, thiourea, or thiourethane group. The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group is separated by more than six carbon atoms from a urethane, urea, thiourea, or thiourethane group, or the urethane, urea, thiourea, or thiourethane group is not present.

[0233] Embodiment 76. The first compound comprises a carboxylic acid functional group according to structure (I), and the second compound comprises an epoxy functional group according to structure (II) in Embodiment 19. The reaction rate between the first compound and the second compound is higher when the first compound contains a carboxylic acid functional group according to structure (I) and the second compound contains an epoxy functional group according to structure (II) compared to the reaction rate when the first compound does not contain a carboxylic acid functional group according to structure (I), wherein the acid functional group is separated by more than six carbon atoms from a urethane, urea, thiourea, or thiourethane group, or does not contain a urethane, urea, thiourea, or thiourethane group, or the second compound does not contain an epoxy functional group according to structure (II), and the epoxy functional group is separated by more than six carbon atoms from a urethane, urea, thiourea, or thiourethane group, or does not contain a urethane, urea, thiourea, or thiourethane group, and / or the first compound does not contain a carboxylic acid functional group according to structure (I) and the second compound does not contain an epoxy functional group according to structure (II), according to any one of embodiments 71 to 75.

[0234] Aspect 77. A method for improving the completeness of reacting a first compound having a carboxylic acid functional group with a second compound having a functional group reactive with the carboxylic acid functional group, wherein the first compound contains a carboxylic acid functional group according to structure (I), and more or all of the carboxylic acid functional groups according to structure (I) react with the functional group reactive with the carboxylic acid functional group of the second compound, compared to using a compound that does not contain a carboxylic acid functional group according to structure (I).

[0235] Aspect 78. A method for improving the solvent resistance of a coating layer derived from a first compound containing a carboxylic acid functional group and a second compound containing a functional group reactive with the carboxylic acid functional group, wherein a coating derived from a first compound containing a carboxylic acid functional group according to structure (I) provides better solvent resistance as reflected by a higher MEK double rub score than a coating derived from a first compound containing a carboxylic acid functional group that does not contain the structure according to structure (I).

Examples

[0236] Aspects of the present disclosure are further illustrated by reference to the following examples. It will be apparent to those skilled in the art that many changes can be made to both the materials and methods without departing from the scope of the present disclosure.

[0237] Example 1: Preparation of Acidic Polyurethane According to the Present Disclosure An acid poly-urethane, PU-1, was prepared according to the formulation in Table 1.

[0238] The contents of Charge 1 were added to a four-neck reaction flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser. After the exotherm subsided, the temperature was raised to 75 °C and held for 4 hours. The NCO equivalent was measured according to ASTM D2572-19 (1331 g / eq, theoretical 1290 g / eq). The reaction product was cooled to 65 °C. Charge 2 was added and the reaction product was allowed to exotherm. When the exotherm subsided, the reaction was held at 75 °C until no NCO was detectable as measured by transmission Fourier transform infrared (FTIR) spectroscopy. Charge 3 was added to obtain a final polyurethane having a measured solids content of 49.8 wt% and a measured acid value of 107 mg KOH / g on the resin solids.

Table 1

[0239] Example 2: Preparation of Acidic Polyurethane PU-2 According to the Present Disclosure Acidic polyurethane, PU-2, was prepared according to the formulations shown in Table 2.

[0240] The contents of input 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and heated to 55°C. Input 2 was supplied for 1 hour while maintaining the exothermic temperature below 75°C. The reaction was held at 75°C until NCO became undetectable, as measured by transmission Fourier transform infrared (FTIR) spectroscopy. Volatile components were removed under vacuum distillation to obtain the final polyurethane with a measured acid value of 154 mg KOH / g. [Table 2]

[0241] Example 3: Preparation of acidic polyurethane according to the present disclosure PU-3 24 Acidic polyurethane, PU-3, was prepared according to the formulations shown in Table 3.

[0242] The contents of input 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and heated to 70°C. Input 2 was supplied for 45 minutes while maintaining the exothermic temperature below 75°C. The reaction was held at 80°C until NCO became undetectable, as measured by transmission Fourier transform infrared (FTIR) spectroscopy. Volatile components were removed under vacuum distillation to obtain the final polyurethane with a measured acid value of 187 mg KOH / g. [Table 3]

[0243] Example 4: Preparation of comparative acidic polyester PE-1 Acidic polyester, PE-1, was prepared according to the formulations shown in Table 4.

[0244] The contents of inputs 1 and 2 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser. The reaction mixture was heated to 100°C and held for 30 minutes. The temperature was then increased to 140°C and held at 140°C until the anhydrous material became undetectable as measured by transmission Fourier transform infrared (FTIR) spectroscopy. The final polyester had a measured acid value of 258 mg KOH / g. [Table 4]

[0245] Example 5: Preparation of epoxy polyurethane PU-4 Epoxy polyurethane, PU-4, was prepared according to the formulations shown in Table 5.

[0246] The contents of input 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and heated to 80°C. Input 2 was supplied while maintaining the exothermic temperature below 90°C. The reaction was held at 90°C until NCO became undetectable, as measured by transmission Fourier transform infrared (FTIR) spectroscopy. The final polyurethane had a measured solid content of 43.6% by weight and a measured epoxy equivalent of 339 g / eq on the resin solid. [Table 5]

[0247] Example 6: Preparation of acidic polyurethane dispersion according to the present disclosure PUD-1 A polyurethane dispersion (PUD-1) was prepared according to the formulations shown in Table 6.

[0248] The contents of Charge 1 were added to a four-neck reaction flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser. After the exotherm subsided, the temperature was raised to 80 °C and held for 3 hours. The NCO equivalent was measured (1286 g / eq, theoretical 1290 g / eq). The reaction mixture was cooled to 50 °C. Charge 2 was added and the reaction mixture was allowed to exotherm. When the exotherm subsided, the reaction was held at 65 °C until the NCO level became undetectable as measured by Fourier transform infrared (FTIR) spectroscopy. Charge 3 was added. The reaction mixture was heated to 80 °C and held until the cyclic anhydride became undetectable via FTIR. An aqueous dispersion was prepared by adding Charge 4 and Charge 5. The final dispersion had a measured solids content of 37.7 wt% and a measured acid value of 87 mgKOH / g on resin solids.

Table 6

[0249] Example 7: Preparation of an acidic polyurethane dispersion PUD-2 according to the present disclosure A polyurethane dispersion (PUD-2) was prepared according to the formulation in Table 7.

[0250] The contents of Charge 1 were added to a four-neck reaction flask equipped with a stirrer, a gas inlet, a thermometer, and a condenser and heated to 50 °C to allow the reaction mixture to exotherm. After the exotherm subsided, the reaction was held at 75 °C for 1 hour. The NCO equivalent was measured (theoretical 1268 g / eq, measured 1391 g / eq). The reaction mixture was cooled to 50 °C by adding Charge 2. Charge 3 was added, followed by Charge 4, and the reaction was allowed to exotherm. When the exotherm subsided, the reaction was held at 60 °C until the NCO became undetectable as measured by FTIR. Charge 5 was added and the reaction was held at 80 °C until the anhydride peak did not change as measured by FTIR. The final polyurethane had a measured solids content of 74.2 wt% and a measured acid value of 93.3 mg / KOH on resin solids.

Table 7

[0251] Example 8: Preparation of acidic polyurethane dispersion according to the present disclosure PUD-3 A polyurethane dispersion (PUD-3) was prepared according to the formulations shown in Table 8.

[0252] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser. After the exothermic reaction subsided, the temperature was raised to 80°C and held for 3 hours. The NCO equivalent was measured (1831 g / eq, theoretical 1799 g / eq). The reaction mixture was cooled to 50°C. Addition 2 was added, and the reaction mixture was exothermic. After the exothermic reaction subsided, the reaction was held at 65°C until NCO was undetectable, as measured by FTIR. Addition 3 was added. An aqueous dispersion was prepared by adding Addition 4. The final dispersion had a measured solid content of 38.1% by weight and a measured acid value of 75 mg KOH / g on the resin solid. [Table 8]

[0253] Example 9: Preparation of polyurethane dispersion according to the present disclosure PUD-4 A polyurethane dispersion (PUD-4) was prepared according to the formulations shown in Table 9.

[0254] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and the reaction was heated to 50°C to generate heat. After the heat generation subsided, the reaction was held at 75°C for 6 hours. The NCO equivalents were measured (theoretical 1799 g / eq, measured 1959 g / eq). The reaction was cooled to 50°C by adding Addition 2. Addition 3, followed by Addition 4, was added, and the reaction was generated again. After the heat generation subsided, the reaction was held at 65°C until NCO was undetectable as measured by FTIR. The final polyurethane had a measured solid content of 56.0 wt% and a measured acid value of 78.1 mg / KOH on the resin solid. [Table 9]

[0255] Example 10: Preparation of polyurethane dispersion according to the present disclosure PUD-5 Polyurethane was prepared according to the formulations shown in Table 5.

[0256] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser. After the exothermic reaction subsided, the temperature was raised to 80°C and held for 5 hours. The NCO equivalent was measured (1350 g / eq, theoretical 1290 g / eq). Addition 2 was added and the reaction was held at 80°C until NCO became undetectable as measured by FTIR. Aqueous dispersions were prepared by adding Additions 3 and 4. The final dispersion had a measured solid content of 38.9% by weight and a theoretical acid value of 108 mg KOH / g on the resin solid. [Table 10]

[0257] Example 11: Preparation of polyurethane dispersion according to the present disclosure PUD-6 A polyurethane dispersion (PUD-6) was prepared according to the formulations shown in Table 11.

[0258] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser. After the exothermic reaction subsided, the temperature was raised to 75°C and maintained for 5 hours. The NCO equivalent was measured (1312 g / eq, theoretical 1290 g / eq). The reactants were cooled to 65°C. Addition 2, followed by Addition 3, was added. The reaction was maintained at 75°C until NCO was undetectable, as measured by IR. Aqueous dispersions were prepared by adding Addition 4 and Addition 5. The final dispersion had a measured solid content of 44.3 wt% and a theoretical acid value of 101 mg KOH / g on a resin solid. [Table 11]

[0259] Example 12: Preparation of carbodiimide Carbodiimide was prepared according to the formulations shown in Table 12.

[0260] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and heated to 160°C. The reaction was held until the measured isocyanate value exceeded 384 g / eq. The reaction mixture was cooled to room temperature and accelerated by adding Addition 2. The resulting NCO prepolymer had a measured isocyanate value of 532 g / eq and 66.3 wt% solid content. The NCO prepolymer and a portion of Addition 3 were heated to 70°C and held for 1 hour. Addition 4, followed by Addition 5, was added, and the reaction was held at 80°C until NCO was undetectable by IR analysis. The reaction mixture was dispersed by adding Addition 6. The dispersed material had a solid content of 34.2 wt% and a theoretical carbodiimide equivalent of 646 g / eq on the resin solid. [Table 12]

[0261] Example 13: Preparation of epoxy polyurethane PU-5 Epoxy polyurethane, PU-5, was prepared according to the formulations shown in Table 13.

[0262] The contents of Addition 1 were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser, and heated to 80°C. Addition 2 was added dropwise. The reaction mixture was heated to 90°C. After the exothermic reaction subsided, the reaction was held at 90°C until NCO became undetectable, as measured by transmission Fourier transform infrared (FTIR) spectroscopy. Volatile components were removed under vacuum distillation to obtain a final polyurethane with a measured epoxy equivalent of 362 g / eq. [Table 13]

[0263] Example 14: Preparation of epoxy urethane PU-6 Epoxy polyurethane, PU-6, was prepared according to the formulations shown in Table 14.

[0264] The contents of input 1, followed by input 2, were added to a four-necked reaction flask equipped with a stirrer, gas inlet, thermometer, and condenser. The reaction mixture was heated to 80°C. After the exothermic reaction subsided, the reaction was maintained at 80°C until NCO became undetectable, as measured by transmission Fourier transform infrared (FTIR) spectroscopy. As a result, a final polyurethane was obtained with a measured solid content of 83.8% by weight on the resin solid and an epoxy equivalent of 191 g / eq. [Table 14]

[0265] Example 15: Liquid coating curable composition Example (Ex.): A transparent coating composition was prepared by mixing side A and side B. For side A, the components listed in Table 15 were weighed, placed in a scintillation vial, and mixed until homogeneous. For side B, the components listed in Table 15 were weighed and placed in a separate scintillation vial. Unless otherwise specified, all material amounts are in weight percentages. [Table 15]

[0266] Prior to coating application, the corresponding amounts of formulation A and formulation B shown in Table 16 were mixed and thoroughly combined. The formulations were applied using an 8-mil gap square applicator onto a 4-inch x 12-inch steel substrate pre-coated with ED7100 Electrocoat Primer (available from ACT Test Panels LLC (Hillsdale, MI)). The coated panels were flashed at ambient conditions for 10 minutes and then baked in a 60°C oven for 45 minutes. Each coated panel was left at ambient conditions for 7 days before being subjected to solvent resistance testing (Table 17). [Table 16] [Table 17]

[0267] As shown in Table 17, Ex.A, which contains PU-1, achieves a higher MEK DR of 64 when cured with Denacol EX-622 than Ex.C, which does not contain an acid close to the urethane and has a MEK DR of 4. Furthermore, Ex.B, which contains PU-1, achieves a higher MEK DR of 100+ when cured with PU-4 than Ex.D, which does not contain an acid close to the urethane and has a MEK DR of 66.

[0268] Example 16: Powder-coated curable composition The coating formulations Ex.E to I of this disclosure were prepared in the amounts shown in Table 18 using the following method. All values ​​in Table 18 are given in grams by weight.

[0269] Powder gelation time: The gelation time was determined according to the test method described in ASTM D4217-07. The interval (mm:ss = minutes:seconds) during which the coating powder changed from a dry solid to a gel state was measured on a polished, high-temperature surface at the temperatures specified in Table 18.

[0270] All reactions were carried out on a hot plate set to either 180°C, 150°C, or 130°C. The reactants were placed separately on the hot plate and allowed to melt or soften. They were then mixed together, and a timer was set. When the materials gelled or solidified, the timer was stopped, and the elapsed time was recorded (Table 19). [Table 18] [Table 19]

[0271] As can be seen in Table 19, Ex.E, which contains PU-2, gels in 20 seconds, compared to 1 minute for Ex.F, which is close to urethane and does not contain acid. Both formulations were reacted with the same common crosslinker used in powder coatings, triglycidyl isocyanurate (TGIC). Furthermore, even at curing temperatures as low as 150°C, Ex.E gels in 1 minute and 15 seconds, more than four times faster than Ex.F.

[0272] As shown in Table 19, Ex.G, which contains PU-2, gels in 1 minute, compared to 1 minute and 50 seconds for Ex.H, which is close to urethane and does not contain acid. Both formulations were reacted with the same common crosslinker used in powder coating, hydroxyalkylamide (Primid XL552). Furthermore, even at curing temperatures as low as 150°C, Ex.G gels more than twice as fast as Ex.H, in 6 minutes.

[0273] Furthermore, considering Ex I, it was observed that the combinations of PU-2 and PU-5, which include an acid close to the urethane and an epoxy close to the urethane, showed the fastest gelation time and could gel even at 130°C, demonstrating a significant advantage to the combination of an acid close to the urethane and an epoxy close to the urethane.

[0274] Example 17: Liquid curable composition Formula Ex.JM was prepared in the quantities shown in Table 20 using the following method. All values ​​in Table 20 are given in parts by weight. The acid-containing material was dissolved in Dowanol® PM glycol ether (available from Dow Chemical Company, Midland, MI, USA), and then the epoxy-containing material and DABCO33LV (available from Sigma-Aldrich Inc., St. Louis, MO, USA) were added and mixed. For each mixture, the initial acid value and epoxy equivalent were recorded. 5.0 grams of material were weighed into a 70 mm diameter aluminum pan. The pan was baked in an oven at 100°C for 1 hour and left at ambient conditions for a further 1 day. The wt% solid of the reactive composition was then calculated based on the total residual mass, acid value (mg KOH), and epoxy equivalent (g / eq) compared to a known starting composition solid (Table 21). [Table 20]

[0275] The percentage conversion rate was calculated from the normalized acid value and epoxy equivalent of the reactant solids, compared to the initial solid values. [Table 21]

[0276] When PU-6 was reacted with an acid close to the urethane, a higher reaction conversion rate was observed compared to Ex.K, which did not contain an acid close to the urethane, regardless of monitoring of acid value or epoxy equivalent. A similar advantage was observed when the acid close to the urethane in Ex.L reacted with Eponex 1510 compared to the acid not close to the urethane in Ex.M. Furthermore, when the acid close to the urethane was reacted with an epoxy close to the urethane in Ex.J, the highest reaction conversion rate was observed, indicating that having urethane close to both epoxy and acid provides the highest reaction conversion rate.

[0277] Example 18: Curable composition containing carbodiimide A curable composition was prepared according to the formulations shown in Table 22. After mixing the polyurethane dispersion, water, and silicone surfactant in a 20 ml glass scintillation vial, Carbodilite V-02-L2 (available from Nisshinbo Chemical) was added and thoroughly stirred. The formulation was sprayed using a SataJet 4000 B HVLP with a WSB fluid tip onto a 4-inch x 12-inch steel substrate pre-coated with ED7100 electrocoat primer (available from ACT Test Panels LLC (Hillsdale, MI)) treated and baked according to the manufacturer's recommendations. The film was flashed at ambient conditions for 15 minutes and then baked in a 60°C oven for 40 minutes. Each coated panel was left at ambient conditions for 7 days before being subjected to solvent resistance testing. [Table 22]

[0278] Example 19: Curable composition containing epoxy A curable composition was prepared according to the formulations shown in Table 23.

[0279] After mixing the polyurethane dispersion, water, and silicone surfactant, Denacol EX 614B (available from Nagase America LLC) was added and thoroughly stirred. Formulations D–F were applied using an 8-mil gap square applicator on a 4-inch × 12-inch steel substrate pre-coated with ED6421HE electrocoat primer (available from ACT Test Panels LLC (Hillsdale, MI)) or ED7100 electrocoat primer (available from ACT Test Panels LLC (Hillsdale, MI)). The film was flashed at ambient conditions for 15 minutes and then baked in an oven at 140°C for 60 minutes. Example G was applied using a #26 wired drawdown bar on a 0.0080-inch thick 5182-H48 aluminum substrate pre-treated with Cr-VI Henkel 702 pre-treatment (available from Alcoa Weirton, WV). Next, the coatings were immediately placed in a Hendinair oven set to 281°C, a belt speed of 51 rpm, and a fan speed of 9 rpm. Using the Hendinair oven settings, a peak metal temperature of 240°C was achieved for 10 seconds. Each coated panel was left at ambient conditions for 7 days before being subjected to solvent resistance testing, as shown in Table 26. [Table 23]

[0280] Example 20: Curable composition containing oxazoline A curable composition was prepared according to the formulations shown in Table 24.

[0281] A polyurethane dispersion, water, and silicone surfactant were mixed in a 20 ml glass scintillation vial, and then Epocros WS-500 (available from Nippon Shokubai CO.LTD.) was added and thoroughly stirred. The formulation was applied using an 8 mil gap square applicator onto a 4-inch x 12-inch steel substrate pre-coated with ED6421HE electrocoat primer (available from ACT Test Panels LLC (Hillsdale, MI)), which had been treated and baked according to the manufacturer's recommendations. The film was flashed at ambient conditions for 15 minutes and then baked in a 100°C oven for 45 minutes. Each coated panel was left at ambient conditions for 1 day before being subjected to solvent resistance testing. [Table 24]

[0282] Example 21: Curable composition containing aziridine A curable composition was prepared according to the formulations shown in Table 25.

[0283] Polyurethane, NeoAdd PAX-523 (available from Covestro AG), and methyl ethyl ketone were mixed and thoroughly stirred. The formulation was applied using an 8 mil gap square applicator onto a 4-inch x 12-inch steel substrate pre-coated with ED7100 electrocoat primer (available from ACT Test Panels LLC (Hillsdale, MI)), which had been treated and baked according to the manufacturer's recommendations. The film was flashed at ambient conditions for 5 minutes and then baked in an oven at 140°C for 30 minutes. Each coated panel was left at ambient conditions for 7 days before being subjected to solvent resistance testing. [Table 25]

[0284] Example 22: Curable composition properties Solvent resistance tests were performed on the curable compositions of each example in Tables 22-25 using the procedure described above. The results of the solvent resistance tests, recorded in the MEK double lab, can be seen in Table 26 below. [Table 26]

[0285] As can be seen in the above examples, curable compositions were prepared using various polyurethanes containing acidic functional groups adjacent to the urethane, exhibiting excellent solvent resistance as demonstrated by solvent resistance tests. Furthermore, it was demonstrated that acidic functional groups adjacent to the urethane can be introduced using various synthetic approaches, all of which result in a curable portion. In addition, several different curing agents or crosslinkers with reactivity to the acidic functional groups were demonstrated as part of the curable composition.

[0286] Example 23: Reactive composition Formulas Ex.Z~CC were prepared in the amounts shown in Table 27 using the following method. All values ​​in Table 27 are given in parts by weight. The acid-containing material was dissolved in dimethyl sulfoxide-d6, followed by the addition of the epoxy-containing material and catalyst, DABCO 33LV (available from Sigma-Aldrich Inc., St. Louis, MO, USA). The resulting formulations were mixed on a vortex mixer, transferred to 5 mm NMR tubes, and analyzed on a Bruker AVIII HD 500 MHz NMR (nuclear magnetic resonance) instrument at 100 °C. Proton NMR was collected as the reaction proceeded (16 scans, 15-second relaxation delay). At least 14 data points were collected for each formulation to obtain relative rate constants. Note that the signal for each data point is the average of 16 scans. For Ex.Z and Ex.BB, the absolute integral of the epoxy peak signal at 3.1 ppm (corresponding to the methine proton in the epoxy ring) was monitored. For Ex.AA and Ex.CC, the absolute integral of the epoxy peak signal at 2.8 ppm (corresponding to the methylene proton in the epoxy ring) was monitored. These signals were selected for analysis because they had minimal signal overlap with other protons in the system. The decrease in the absolute integral with respect to time was plotted and fitted to a first-order exponential decay curve. [A] = [A] o e -k app t In the equation, [A] is the absolute integral of the signal corresponding to the epoxy ring-opening reaction. Therefore, the apparent rate constant k app (s -1 ) can be easily obtained from the curve fitting (Table 28), and therefore the k of the four formulations app This enables relative comparisons between different segments. [Table 27] [Table 28]

[0287] As shown in Table 28, acids close to urethane (Ex. Z) react faster with epoxy than acids not close to urethane (Ex. BB). Similarly, acids close to urethane (Ex. AA) react faster with epoxy not close to urethane than acids not close to urethane (Ex. CC). Furthermore, when the acid is close to the urethane and the epoxy is also close to the urethane, the relative reaction is shown to be the fastest, as indicated in Ex. Z.

[0288] While specific examples of compositions and methods provided herein are given above for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications can be made to the details of this disclosure without departing from the disclosure as defined in the appended claims.

Claims

1. structure: 【Chemistry 1】 A first compound containing 1 to 12 carboxylic acid functional groups according to, wherein R １ is C １ to C ６ , for example, C １ to C ４ , or C １ to C ３ is a linear or branched alkyl group, X is O, S or NR ２ , and R ２ is H, methyl, ethyl, propyl or isopropyl, and a first compound, A reactive composition comprising a second compound containing a functional group that is reactive with the carboxylic acid functional group in the first compound.

2. The first compound comprises a polymer backbone and / or a base molecule containing 6 to 60, for example, 6 to 50 or 6 to 40 linear, branched, cyclic and / or aromatic carbon atom molecular chains, and optionally O, S or NR ５ It can contain heteroatoms including R ５ The carboxylic acid functional group is H, methyl, ethyl, propyl or isopropyl, and the carboxylic acid functional group includes terminal groups and / or pendant groups from the polymer backbone and / or the base molecule, and / or The reactive composition according to claim 1, wherein the base molecule optionally comprises a cyclic portion comprising 5 to 14 ring units, for example, 6 to 12 or 6 to 10 ring units, wherein optionally some of the ring units comprise heteroatoms and the remaining ring units comprise carbon.

3. The reactive composition according to claim 1 or 2, wherein the first compound comprises a polymer containing a carboxylic acid group having an acid value of 10 mg KOH to 250 mg KOH, for example, 20 mg KOH to 225 mg KOH, or 25 mg KOH to 200 mg KOH, on a solid basis according to ASTM D4662-15.

4. The reactive composition according to any one of the prior claims, wherein the carboxylic acid functional group is a reaction product of an isocyanate and a compound comprising a carboxylic acid group and a hydroxyl, a carboxylic acid group and a thiol, and / or a carboxylic acid group and an amine.

5. The reactive composition according to any one of the prior claims, wherein the first compound is present in the composition in an amount of 10% to 85% by weight, for example, 15% to 85% by weight, or 20% to 80% by weight, or 30% to 80% by weight, or 30% to 70% by weight, or 40% to 70% by weight, or 50% to 80% by weight, or 60% to 70% by weight, and the weight percentage is based on the total resin solid of the composition.

6. The reactive composition according to any one of the prior claims, wherein the second compound comprises a carbodiimide, epoxy, hydroxyl, thiol, primary amine, secondary amine, hydroxylamine, oxazoline, hydroxyalkylamide, hydroxyalkylurea, and / or aziridine functional group.

7. The second compound is as follows: 【Chemistry 2】 The compound comprises an epoxy-functional compound having a structure according to the formula, where R １ However, C １ ~C ６ For example, C １ ~C ４ , or C １ ~C ３ It is a linear or branched alkyl group, where X is O, S, or NR ２ And R ２ However, it is H, methyl, ethyl, propyl, or isopropyl. Each R ３ and R ４ However, independently, H and C １ ~C ５ The base molecule may consist of a linear or branched alkyl group, 6 to 60, for example, 6 to 50 or 6 to 40 linear, branched, cyclic, and / or aromatic carbon atom molecular chains, and / or polymer backbone, and may optionally contain O, S, or NR ５ It can contain heteroatoms including R ５ However, H is methyl, ethyl, propyl, or isopropyl, and optionally one R ３ and R ４ However, it can form a polymer backbone and / or part of a base molecule containing 6 to 60, for example, 6 to 50 or 6 to 40 linear, branched, cyclic, and / or aromatic carbon atom molecular chains. Each R ３ and R ４ However, independently, as needed, O, S, or NR ６ It can contain heteroatoms including R ６ However, it is H, methyl, ethyl, propyl, or isopropyl, The reactive composition according to any one of the prior claims, wherein the epoxy-functional compound comprises terminal groups and / or pendant groups from the polymer backbone and / or the base molecule.

8. The reactive composition according to any one of the prior claims, wherein the first compound and / or the second compound comprises a polymer containing a urethane, urea, thiourea, or a thiourethane repeating group, a (meth)acrylate repeating group, an ester repeating group, an amide repeating group, and / or a carbonate repeating group.

9. The reactive composition according to any one of the prior claims, wherein the second compound is present in the composition in an amount of 15% to 90% by weight, for example, 15% to 85% by weight, or 20% to 80% by weight, or 30% to 80% by weight, or 30% to 70% by weight, or 40% to 70% by weight, or 50% to 80% by weight, or 60% to 70% by weight, and the weight percentage is based on the total resin solid of the composition.

10. Contains a catalyst, The catalyst comprises zinc, phosphine, amine, quaternary ammonium group, phosphonium, and / or quaternary phosphonium group, and / or The reactive composition according to any one of the prior claims, wherein the catalyst is present in an amount of 0.05% to 2% by weight, or 0.1% to 1.5% by weight, or 0.25% to 1% by weight, and the weight percentage is based on the weight of the reactive composition.

11. The reactive composition according to any one of the prior claims, wherein the reactive composition is a curable composition, the first compound comprises two or more carboxylic acid groups, and / or the second compound comprises two or more functional groups that are reactive with the carboxylic acid functional groups.

12. A reactive composition according to any one of the prior claims in the form of a liquid composition, wherein the liquid composition is liquid under ambient conditions and solvent-free, or the liquid composition comprises 20 to 80% by weight of a solvent, for example, 30 to 70% by weight of a solvent, or 40 to 60% by weight of a solvent, based on the weight of the reactive composition, wherein the solvent comprises water and / or an organic solvent, and optionally the reactive composition comprises a neutralizing amine at a total neutralization level of 40 to 120%, or 40 to 80%, or 40 to 90%, or 60 to 100%, or 80 to 90%, based on the number of acidic groups in the reactive composition.

13. A reactive composition according to any one of the prior claims, which reacts to form a reaction product as a component of the composition.

14. The reaction product has a molecular weight of less than 2,000 g / mol, for example, less than 1,500 g / mol, or less than 1,000 g / mol, or less than 750 g / mol, or less than 500 g / mol. The reaction product may optionally include a chiral center, stereoisomers, enantiomers, and / or diastereomers, and / or The reactive composition according to claim 13, wherein the reaction product is, if necessary, a racemic mixture.

15. The reactive composition according to claim 13, wherein the reaction product is a polymer having a weight-average molecular weight of more than 2,000 to 50,000, for example, 2,500 to 40,000, or 3,000 to 30,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard.

16. A method for coating a substrate, comprising: applying a reactive composition according to any one of claims 1 to 12 to at least a portion of the substrate using spray coating, roller coating, coil coating, dip coating, precision coating, or spin coating techniques; and curing the reactive composition to form a cured layer. The cured layer is, if necessary, part of a multilayer coating, and the cured layer includes a primer coat, a base coat or color coat layer, and / or a clear coat layer. The reactive composition is reacted at a temperature of 0°C to 260°C, or 20°C to 240°C, or 40°C to 225°C, or 60°C to 225°C, or 80°C to 215°C, or 100°C to 215°C, for 5 seconds to 168 hours, for example, 5 seconds to 48 hours, or 5 minutes to 24 hours, or 10 minutes to 12 hours, or 10 minutes to 12 hours, or 20 minutes to 12 hours, or 15 minutes to 12 hours. A method in which, if necessary, the reactive composition is flashed for 5 to 60 minutes, for example 5 to 30 minutes, at a temperature of 10°C to 80°C, for example 20°C to 60°C, for example 20°C to 40°C, before reacting.

17. The reactive composition reacts when less energy is applied, for example, at a lower temperature, than a composition that does not contain the compound containing the carboxylic acid functional group according to structure (I), and / or The reactive composition reacts faster at the same temperature than a composition that does not contain a compound comprising the carboxylic acid functional group according to the structure (I) described in claim 1, and / or The reactive composition reacts when less energy is applied, for example at a lower temperature, than a composition comprising a first compound comprising structure (I) and a second compound comprising structure (II), and not comprising a compound comprising the carboxylic acid functional group according to structure (I), or comprising the carboxylic acid functional group according to structure (I), but not comprising the second compound comprising structure (II) as described in claim 7, and / or The method according to claim 16, wherein the reactive composition reacts faster at the same temperature than a composition that does not contain a compound containing the carboxylic acid functional group according to structure (I), or a composition that contains the carboxylic acid functional group according to structure (I) but does not contain a second compound containing structure (II).

18. The method according to claim 16 or 17, wherein the reactive composition is applied to at least a portion of a substrate to form an article.

19. A manufactured article produced by ambient reactive extrusion comprising the reactive composition according to any one of claims 1 to 15, The reactive composition is coated in multiple layers, The first reactive composition is applied as the first layer. The second reactive composition is applied to the surface of the first reactive composition to form a second layer, and / or A manufactured article in which the article forms at least part of a structure such as a vehicle, a manufactured article, a consumer electronic device, a consumer electrical appliance, pavement, road marking, or a component of a modular housing.

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