Water-based coating composition

Abstract

To develop an aqueous primer composition that exhibits properties comparable to those of existing solvent-based primers. [Solution] Water, a) (a1) a binder containing a core-shell latex copolymer having a pendant carbonyl group, and b) (b1) formula -C(=O)-NH-N(R h )(R i )(wherein, R h and R i These are independently H or C1-C 12 An aqueous coating composition comprising a crosslinking agent containing at least one polyhydrazide compound having at least two hydrazide groups (which are alkyl), wherein the molar ratio of hydrazide groups to carbonyl groups in the composition is 5:1 to 1:5.

Description

[Technical Field]

[0001] The present invention relates to an aqueous coating composition comprising a binder containing a core-shell latex copolymer having pendant carbonyl groups, and a crosslinking agent containing at least one polyhydrazide compound having at least two hydrazide groups. The coating composition is particularly useful as a primer in the refinishing of automobiles. [Background technology]

[0002] The term "automotive refinishing" refers to the compositions and processes used to repair the finish of a damaged automobile, typically, but not always, the finish provided by the original equipment manufacturer (OEM). Damaged automotive parts will contain defective areas where the previously applied coating layer has been removed, and such removal may, under certain circumstances, expose the bare substrate of the part. Therefore, refinishing operations may involve the repair or replacement of the entire damaged automotive body part, the repair of one or more coating layers applied to the part, or a combination of both operations. The size of the defective area and the presence or absence of a surrounding coating (which, if present, can act as an anchor to the refinishing coating composition) are often determinants of the type of operation performed. Regarding the repair of a coating layer, the refinishing process generally includes a series of steps: sanding the surface to be refinished; applying at least one coat of a primer composition; optionally sanding the applied primer composition; applying at least one base coat to achieve a desired visual appearance, such as a desired color, gloss, or distinctness of image (DOI); and optionally applying a clear coat composition. As used herein, the term “primer” is intended to encompass both primer and primer undercoat. Furthermore, as used herein, “topcoat” refers to any protective or decorative coating applied over the primer coating layer in a refinishing operation, including but not limited to tie coat, base coat, colored base coat, and clear coat. A primer coating layer is applied to promote adhesion between the substrate surface and the subsequent coating layer. Furthermore, the primer coating layer can enhance the overall physical properties of the coating system, particularly its corrosion resistance and impact strength. Additionally, the primer coating layer can contribute to the overall appearance of the coating system by providing a smooth layer upon which subsequent layers can be applied.

[0003] Historically, primer coating compositions have been solvent-based and therefore contain a considerable amount of volatile organic compounds (VOCs). However, due to environmental concerns, there is a regulatory movement to reduce the levels of such VOCs, particularly in automotive refinish coatings. For example, in the United States, Section 183(e) of the Clean Air Act sets VOC emission standards, and for mandatory emission levels for automotive refinish coatings, refer to 42 United States Code (USC) 7511b(e) and 40 Code of Federal Regulations (CFR) Part 59, Subpart B. One mechanism for reducing VOC content is the use of so-called "high solids" primer compositions in which the level of organic solvent relative to the mass of the binder and any coexisting pigments and fillers is reduced. The problem is that high viscosity is an inevitable consequence of high solids content, which relates to the difficulty of applying the composition. Low fluidity of the composition limits the ways in which such a composition can be applied, and may result in no leveling effect of the composition applied on the substrate surface. A second mechanism for reducing VOC content is to use an aqueous composition. For example, U.S. Patent No. 8,461,253 (Ambrose et al.) describes an aqueous coating composition comprising (a) acrylic copolymer resin particles containing pendant carbonyl functional groups, (b) a crosslinking agent containing at least two functional groups that are reactive to the carbonyl functional groups of the acrylic copolymer, and (c) a non-reactive surfactant, wherein the acrylic copolymer resin particles are prepared in a single-step polymerization process and have a calculated minimum glass transition temperature (Tg) of 40°C.

[0004] However, aqueous compositions may exhibit insufficient moisture resistance, insufficient corrosion resistance, and may have poor or non-permanent adhesion to metal substrate surfaces. Aqueous primer compositions must be thoroughly dehydrated for proper crosslinking and curing to occur. Given their boiling points, complete removal of water can be difficult to achieve through flash drying. Removing water traditionally requires very strict heating and drying conditions, with careful control of air movement and humidity in the oven or drying booth. Therefore, drying can be an energy burden and may interfere with the refinishing process. However, insufficient drying can lead to blistering, popping, and pinhole formation as trapped moisture escapes from the cured coating. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 8,461,253 [Patent Document 2] U.S. Patent No. 7,825,173 [Patent Document 3] European Patent No. 0520426 [Patent Document 4] European Patent No. 1784463 [Non-patent literature]

[0006]

Non-Patent Document 1

Summary of the Invention

[0007] There is a desire to develop an aqueous primer composition that exhibits properties comparable to those of prior solvent-based systems. More specifically, the aqueous primer composition should exhibit good leveling on the application surface and be dehydratable (upon application) under mild or low heat drying conditions. The cured primer coating should further be substantially free of blisters, pops, or pinholes. According to a first aspect of the present disclosure, water, and a) (a1) a core-shell latex copolymer having pendant carbonyl groups, the core-shell latex copolymer including a core copolymer and a shell copolymer disposed around the core copolymer, each of the core copolymer and the shell copolymer independently being i) of formula MA: H2C=CG a CO2R a (MA) (wherein G a is hydrogen, halogen, or methyl, and R a is C1-C 18 alkyl; C2-C 18 heteroalkyl; C3-C 18 cycloalkyl; C2-C8 heterocycloalkyl; C2-C8 alkenyl; C2-C8 alkynyl; C6-C 18 aryl, C1-C9 heteroaryl, C7-C 18 alkoxyaryl, C7-C 18 alkaryl, or C7-C 18 aralkyl) represented by at least one (meth)acrylate monomer, and optionally, ii) at least one vinyl aromatic monomer, Optionally, iii) at least one monomer having at least two ethylenically unsaturated groups and having a maximum mass-average molecular weight (Mw) of approximately 600 daltons, Optionally, iv) at least one hydroxyl-functionalized ethylenically unsaturated monomer It contains the residue, At least one of the core copolymer and the shell copolymer is v) at least one carbonyl-functionalized ethylenically unsaturated monomer A core-shell latex copolymer containing the residues of, Binders, including b) At least two equations -C(=O)-NH-N(R h )(R i )(wherein, R h and R i These are independently H or C1-C 12 A polyhydrazide compound having an alkyl hydrazide group (at least one polyhydrazide compound) Crosslinking agent containing an aqueous coating composition comprising, A coating composition is provided in which the molar ratio of hydrazide groups to carbonyl groups in the composition is about 5:1 to about 1:5.

[0008] A second aspect of this disclosure provides a cured product obtained from an aqueous coating composition as defined above and in the appended claims. The cured product exhibits excellent drying properties, characterized by the absence of blistering, popping, and pinholes in the coating. Furthermore, the cured product exhibits excellent adhesion to the surface of a metal substrate, and as a result, the product can be subjected to gentle sanding without delamination or adhesive failure. The Disclosure also provides an article comprising a metal substrate and a multilayer coating disposed on the metal substrate, wherein at least one layer of the multilayer coating comprises a cured product as defined above and in the appended claims. In key embodiments of the article, the multilayer coating comprises a primer layer comprising a cured product as defined above and in the appended claims, disposed in direct contact with the substrate; at least one basecoat layer comprising a compound that imparts color and / or visual effect, disposed in direct contact with the primer layer; and a clearcoat layer disposed in direct contact with the at least one basecoat layer.

[0009] Where aspects of this disclosure are described herein as having a particular embodiment, unless otherwise specified, one or more of these embodiments may be incorporated into one of the further embodiments, or combined with one of the further embodiments, even if such combination is not expressly described. In other words, unless otherwise specified, the embodiments described are not mutually exclusive, and their arrangement is within the scope of this disclosure. Various other purposes, advantages, and features of this disclosure will become apparent to those skilled in the art by relating the following discussion to the accompanying drawings. [Brief explanation of the drawing]

[0010] [Figure 1] This figure shows an article according to the first embodiment of the present disclosure. [Figure 2] This figure shows an article according to a second embodiment of the present disclosure. [Modes for carrying out the invention]

[0011] The embodiments for carrying out the invention described below are merely illustrative and not intended to limit the Disclosure or its uses and applications. Furthermore, they are not intended to be bound by the aforementioned background art or any theory presented in the embodiments for carrying out the invention described below. Embodiments of this disclosure generally relate to core-shell latex copolymers, compositions containing the same, and methods for forming the same. For brevity, prior arts relating to the preparation of such polymers and compositions may not be described in detail here. Furthermore, various tasks and process steps described herein may be incorporated into broader procedures or processes having additional steps or functions that are not described in detail here. In particular, various steps in the preparation of such polymers and related compositions are well known, and therefore, for the sake of brevity, conventional steps are described only briefly or omitted entirely without showing the details of well known processes. The polymers and compositions disclosed herein preferably include, consist of, or are essentially composed of the components, elements, and process descriptions described herein. The embodiments disclosed herein for illustrative purposes may preferably be carried out in the absence of any elements not specifically disclosed herein.

[0012] definition The term "essentially consisting of" can describe a variety of non-limiting embodiments that are free from one or more of the arbitrary compounds described herein, or free from one or more additives, solvents, polymers, resins, etc., that are not described herein but are used in the art. The term "approximately" can describe values ​​of ±0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% in various embodiments. Furthermore, in various non-limiting embodiments, all numerical values ​​provided herein should be understood as approximate values ​​with endpoints or specific values, and are intended to be read as "approximately" or "about" the values ​​given, except in actual embodiments. The molecular weights referred to in this specification are typically measured by gel permeation chromatography (GPC) using a polystyrene calibration standard, for example, according to ASTM 3536.

[0013] The "acid value (or acid number)" is a measure of the amount of free acid present in a compound. The acid value is the number of milligrams of potassium hydroxide (mg KOH / g) required to neutralize the free acid present in one gram of the substance. All measured acid values ​​given here are determined according to the German standard DIN 53402. The term "hydroxyl value" as used herein is defined as the mass of milligrams of potassium hydroxide required to neutralize acetic acid when acetylating one gram of a chemical containing free hydroxyl groups. Where specified, the hydroxyl value is analyzed according to the standard test method ASTM D4274-11. Where used herein, the term softening point (°C) used in relation to wax refers to the ring-spherical softening point and, unless otherwise indicated, is measured according to ASTM E28.

[0014] The viscosity of the compositions described herein is measured using a Brookfield viscometer, model DVT2T, under standard conditions of 20°C and 50% relative humidity (RH), unless otherwise specified. The RV spindle set included with the viscometer is used for calibration curve preparation. Measurement of the coating composition is performed using the No. 3 spindle at a rate of 100 revolutions per minute for 1 minute until the viscometer reaches equilibrium. The viscosity reading corresponding to equilibrium is then calculated using the calibration curve. Where mentioned, the calculated glass transition temperature ("T") of the polymer or copolymer. g ") is the Fox formula: 1 / T g,ポリマー ≒Σ i w i / T g,i (In the formula, T g,ポリマー and T g,i(where ∫ and ∫ are the glass transition temperatures of the (co)polymer and component monomer (i), respectively, and wi is the mass fraction of component i.) This is a temperature that can be calculated using [a specific method / function]. The glass transition temperature of a particular homopolymer can be found in published literature.

[0015] When used here, the measured "glass transition temperature" (Tg) is determined by differential scanning calorimetry (DSC) with a heating rate of 20 K / min and midpoint measurement, in accordance with German Industrial Standard (DIN) 53765. Where used herein, the term "minimum film-forming temperature" refers to the lowest temperature required for an aqueous polymer dispersion (latex or emulsion) to bond into a thin film when applied to a substrate. The minimum film-forming temperature (MFFT) is determined here using Rhopoint Industries' BAR-90 in accordance with ASTM D2354-98. Unless otherwise specified, the term "particle size" refers to the longest axis of a particle. For a generally spherical particle, the longest axis is the diameter. "Average volume particle size" (D v When used here, the term 50) means that 50% of the volume of the sampled particles is the given D v The value greater than 50, where 50% of the sampled particles' volume is given by the D value. v This refers to a particle size that corresponds to a value smaller than 50. The particle size is determined here by laser diffraction using Anton Paar's Particle Size Analyzer (PSA) Litesizer 500.

[0016] As used herein, the term "solids content" refers to the mass percentage of non-volatile components in the composition. The solids content can be determined as the inverse of the volatiles content obtained according to the standard test method for volatiles content of ASTM D2369 coatings. When used here, the room temperature is 23°C plus or minus 2°C. As used herein, “ambient conditions” means the ambient temperature and pressure on which the composition is located, or on which the coating layer or the substrate of the coating layer is located. In the context of this disclosure, “multipart composition” is understood to be a composition comprising at least two parts that, due to their (high) reactivity, should be stored in separate containers. The parts are mixed before or during application of the composition, at which point a reaction involving bond formation occurs, typically without additional activation, thereby forming a polymer network. High temperatures may be applied to accelerate the reaction between the parts. As used herein, the term “aqueous composition” refers to the composition that actually comes into contact with the substrate being primed. The term “aqueous” means that the solvent or carrier fluid for the composition mainly or primarily contains water, and as a result, water constitutes at least 50% by mass, for example, at least 60% by mass, or at least 70% by mass, of the liquid continuous phase of the primer composition.

[0017] The term "water-dispersible (co)polymer" as used herein refers to a (co)polymer that exists in the form of particles in water, which are dispersed or suspended and stable against aggregation when further diluted with water. In contrast to water-soluble (co)polymers, a diluted solution (approximately 1 g / L) of a water-dispersible polymer will exhibit scattering when analyzed using dynamic light scattering or any other technique known in the field of particle analysis. The term "water" is used here according to its standard meaning. The water in the coating composition may be distilled water, demineralized water, deionized water, reverse osmosis water, boiler condensate, or ultrafiltered water, and tap water may be acceptable under certain circumstances. As used herein, "curing" of an aqueous coating composition refers to the formation of a coating on a substrate, and curing includes a crosslinking reaction, further encompassing the evaporation (drying) of water from the composition and, if present, cosolvents, and the aggregation of fine particles or dispersed phases of the composition. Such curing can be carried out under ambient conditions or by deliberate exposure to heat and / or irradiation. The degree of curing may be partial or complete, and the degree of crosslinking (%) can be determined, in particular, by dynamic mechanical thermal analysis (DMTA) using TA Instruments' RSA-G2 (FCO, LN2) under an inert gas atmosphere.

[0018] The term "sandpaper" as used herein encompasses sheet materials having abrasive particles supported by a flexible backing, such as cloth, paper, skin, or sheet material. Exemplary abrasive particles include silica, garnet, emery, alumina, alumina-zirconia, and silicon carbide. Sandpaper with a grit of 80-400 is particularly useful in refinishing operations. The term "clear coat" is used here to refer to a coating layer within a multilayer coating that is sufficiently transparent or semi-transparent to allow the underlying coating layer to be seen through it. The term "clear" does not require absolute transparency or semi-transparency. As used herein, “metal” means any type of metal, alloy, or mixture thereof. As used herein, the term “alloy” refers to a substance composed of two or more metals, or a metal and a nonmetal, that are usually melted together and become closely integrated by dissolving into each other in the molten state.

[0019] As used herein, the term "catalytic amount" means an amount of catalyst below the stoichiometric value relative to the reactants, unless otherwise explicitly specified. As used herein, the term “free radical initiator” refers to any chemical species that, when exposed to sufficient energy (e.g., in the form of light or heat), decomposes into two parts that are uncharged but each possess at least one unpaired electron. In particular, free radical thermal initiators generate free radicals through activation by thermal energy, such as heating or irradiation in the infrared or microwave wavelength range. All isomers and chiral options for each compound described herein are explicitly intended for use in various non-limiting embodiments. In polymer synthesis, a distribution of various individual molecules is typically produced, so it will be understood that the subscript of the polymer is usually written as an average value. As used herein, the term "monomer" refers to a substance that can contribute to the chemical structure of a polymer through polymerization reactions. As used herein, the term "monofunctional" refers to having one polymerizable moiety. As used herein, the term "polyfunctional" refers to having more than one polymerizable moiety.

[0020] The term "ethylenically unsaturated monomer," as used herein, refers to any monomer containing a terminal double bond that is polymerizable under the normal conditions of free radical addition polymerization. The term “active hydrogen atom” refers to a hydrogen atom that exhibits activity according to the Zerewitinoff test, as described in Kohlerin J. Am. Chem. Soc., 49, 3181 (1927), which is explicitly incorporated herein by reference as a whole in various non-limiting embodiments. Active hydrogen atoms may originate from hydroxyl, thiol, primary amine, secondary amine, and carboxyl groups. The term "nonionic polyol" used here refers to a polyol that does not contain hydrophilic ionizing groups. The term "blocked" as used here refers to a compound that has reacted with a second compound (which has a "blocking group"), and as a result, the reactive functional group is unavailable until the blocking group is removed. The blocking group can be selectively removed at an appropriate point in the synthetic sequence. Triggering events may include, among others, moisture, heat, or irradiation. Examples of blocked isocyanates include those co-reacted with phenol, methyl ethyl ketoxime, or ε-caprolamtum.

[0021] As used here, "(meth)acrylic" is an abbreviation for "acrylic" and / or "methacrylic." Therefore, the term "(meth)acrylate" collectively refers to acrylate and methacrylate. In this context, the term "keto group" refers to a group in which a carbonyl group is bonded to two carbon atoms. A keto group can be represented by the formula R2C=O (where neither R can be an H). The term "hydrocarbyl group" is used here in its ordinary sense, as is well known to those skilled in the art. When used here, "C1-C n "Alkyl" refers to a monovalent group or part having 1 to n carbon atoms, i.e., an alkane radical, and includes linear and branched organic groups. Therefore, "C1-C 18 "Alkyl" refers to a monovalent group or moiety having 1 to 18 carbon atoms, i.e., an alkane radical, and includes linear and branched organic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and 2-ethylhexyl. In this disclosure, such alkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given moiety (R), one or more non-halogen substituents within the alkyl group are permitted as described herein.

[0022] The "C1-C" used here 18The term "hydroxyalkyl" refers to an HO-(alkyl) group having 1 to 18 carbon atoms, where the substituent bond is through an oxygen atom, and the alkyl group is defined above. An "alkoxy group" refers to a monovalent group represented by -OA (where A is an alkyl group), and non-limiting examples include the methoxy group, ethoxy group, and isopropyloxy group. The "C1-C" used here refers to a monovalent group. 18 The term "alkoxyalkyl" refers to an alkyl group or moiety having the alkoxy substituent defined above, where the (alkyl-O-alkyl) moiety has a total of 1 to 18 carbon atoms. Examples of such groups include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3), and 2-ethoxyethyl. Similarly, the term "C7-C" as used herein refers to an alkyl group or moiety having the alkoxy substituent defined above, where the (alkyl-O-alkyl) moiety has a total of 1 to 18 carbon atoms. 18 The term "alkoxyaryl" refers to an aryl group having the alkoxy substituent defined above, in which the (aryl-O-alkyl) moiety contains a total of 7 to 18 carbon atoms.

[0023] The term "C2-C4 alkylene" used here is defined as a saturated divalent hydrocarbon radical having 2 to 4 carbon atoms. "C3-C 18 The term “cycloalkyl” encompasses saturated, monocyclic or polycyclic hydrocarbon groups or moieties having 3 to 18 carbon atoms. In this disclosure, such cycloalkyl groups or moieties may be unsubstituted or substituted with one or more halogens. Where applicable to a given moiety (R), one or more non-halogen substituents are permitted within the cycloalkyl group, as described herein. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane, and norbornane. The "C3-C" used here 18The term “cycloalkylene” refers to a saturated, divalent monocyclic, bicyclic, or tricyclic hydrocarbon radical having 3 to 18 carbon atoms. In this disclosure, such cycloalkylene moieties may be unsubstituted or substituted with one or more halogens. Where applicable to a given moiety (R), one or more non-halogen substituents are permitted within the cycloalkylene group, as is shown herein. Exemplary C3-C 18 Examples of cycloalkylenes include cyclopropyl-1,1-diyl, cyclopropyl-1,2-diyl, cyclobutyl-1,2-diyl, cyclopentyl-1,3-diyl, cyclohexyl-1,4-diyl, cycloheptyl-1,4-diyl, and cyclooctyl-1,5-diyl.

[0024] When used here, "C6-C" is used alone or as part of a longer part (such as an "aralkyl group"). 18 "Aryl" refers to monocyclic, bicyclic, and tricyclic ring systems in which the monocyclic ring system is aromatic, or at least one of the rings in a bicyclic or tricyclic ring system is aromatic. Examples of bicyclic and tricyclic ring systems include benzo-condensed 2-3 membered carbocyclic rings. In this disclosure, such aryl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given part (R), one or more non-halogen substituents are permitted within the aryl group, as described herein. Examples of aryl groups include phenyl, (C1-C4) alkylphenyl, e.g., tolyl and ethylphenyl, indenyl, naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl, tetrahydroanthracenyl, and anthracenyl. The "C6-C" used here 18The term “arylene group” refers to a divalent radical derived from monocyclic, bicyclic, and tricyclic ring systems having 6 to 18 carbon atoms, wherein the monocyclic ring system is aromatic, or at least one of the rings in a bicyclic or tricyclic ring system is aromatic. The arylene group may be substituted with at least one halogen substituent, but the aromatic portion of the arylene group contains only carbon atoms. Where applicable to a given part (R), one or more non-halogen substituents are permitted within the arylene group, as is shown herein. Exemplary “C6-C 18 Examples of the "arylene" group include phenylene and naphthalene-1,8-diyl.

[0025] In this context, "alkylaryl" refers to an alkyl-substituted aryl group, both of which are defined above. Furthermore, in this context, "aralkyl" refers to an alkyl group substituted with an aryl radical as defined above. When used here, "C2-C 18 "Alkenyl" refers to a hydrocarbyl group or moiety having 2 to 18 carbon atoms and at least one ethylenically unsaturated unit. The alkenyl group or moiety may be linear, branched, or cyclic, and may be substituted with one or more halogens. Where applicable to a given moiety (R), one or more non-halogen substituents are permitted within the alkenyl group, as described herein. The term "alkenyl" also includes radicals having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as understood by those skilled in the art. C2-C 20Examples of alkenyl groups include -CH=CH2, -CH=CHCH3, -CH2CH=CH2, -C(=CH2)(CH3), -CH=CHCH2CH3, -CH2CH=CHCH3, -CH2CH2CH=CH2, -CH=C(CH3)2, -CH2C(=CH2)(CH3), -C(=CH2)CH2CH3, -C(CH3)=CHCH3, -C(CH3)CH=CH2, -CH=CHCH2CH2CH3, -CH2CH=CHCH2CH3, and -CH2CH2C Examples include H=CHCH3, -CH2CH2CH2CH=CH2, -C(=CH2)CH2CH2CH3, -C(CH3)=CHCH2CH3, -CH(CH3)CH=CHCH, -CH(CH3)CH2CH=CH2, -CH2CH=C(CH3)2, 1-cyclopenta-1-enyl, 1-cyclopenta-2-enyl, 1-cyclopenta-3-enyl, 1-cyclohexa-1-enyl, 1-cyclohexa-2-enyl, and 1-cyclohexyl-3-enyl.

[0026] When used here, "C2-C 12 "Alkenylene" refers to a diradical group having 2 to 24 carbon atoms and at least one ethylenically unsaturated unit. Alkenylene radicals may be linear, branched, or cyclic, and may be substituted with one or more halogens. Where applicable to a given portion (R), one or more non-halogen substituents are permitted within the alkenylene radical, as is shown herein. The term "alkenylene" also includes radicals having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as understood by those skilled in the art. The C2-C 12Examples of alkenyl groups, though not limited to them, include etenylene, ethen-1,1-diyl, propenylene, propen-1,1-diyl, propa-2-ene-1,1-diyl, 1-methyl-ethenylene, buta-1-enylene, buta-2-enylene, buta-1,3-dienylene, buten-1,1-diyl, buta-1,3-diene-1,1-diyl, buta-2-ene-1,1-diyl, buta Examples include -3-en-1,1-diyl, 1-methyl-propa-2-en-1,1-diyl, 2-methyl-propa-2-en-1,1-diyl, 1-ethyl-ethenylene, 1,2-dimethyl-ethenylene, 1-methyl-propenylene, 2-methyl-propenylene, 3-methyl-propenylene, 2-methyl-propen-1,1-diyl, and 2,2-dimethyl-ethene-1,1-diyl.

[0027] The term "hetero" as used herein refers to a group or part containing one or more heteroatoms, such as N, O, Si, and S. Therefore, for example, "heterocyclic" refers to a cyclic group having, for example, N, O, Si, or S as part of its ring structure. The "heteroalkyl," "heterocycloalkyl," and "heteroaryl" parts are the alkyl, cycloalkyl, and aryl groups defined above, respectively, that contain N, O, Si, or S as part of their structure. In various embodiments, the term “free from” describes embodiments containing less than about 5, 4, 3, 2, 1, 0.5, or 0.1 mass% of the component, compound, part, functional group, element, or ion in question, using an appropriate mass basis, although this will be understood by those skilled in the art. In other embodiments, the term “free from” describes embodiments having about 0 mass% of the component, compound, part, functional group, element, or ion in question. The term "anhydrous" used here is synonymous with "water-free".

[0028] Referring to the foregoing, the aqueous composition comprises water, a) a binder, and b) a crosslinking agent. The water may be present in an amount of about 10 to about 70% by mass, e.g., about 20 to about 70% by mass, or about 30 to about 60% by mass, based on the mass of the composition. At this water content, drying and bonding of the composition (when applied to a substrate) may not involve significant energy and time costs. Compositions having this water content may be exemplified by a viscosity of less than about 0.05 Pa.s to about 2 Pa.s, about 0.05 to about 1.5 Pa.s, or about 0.05 to about 1 Pa.s, measured at 25°C using a Brookfield viscometer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein. The aqueous compositions of this disclosure may be prepared as one-part (1K) compositions. Alternatively, the aqueous compositions may be prepared as multi-part compositions, wherein at least a core-shell latex copolymer (a1) and a polyhydrazide compound (b1) are provided as separate parts. With respect to multi-part compositions, the constituent water does not need to be independently added to any one or more parts or to the composition itself. Alternatively, one or more parts of the composition may be provided in water.

[0029] In certain embodiments, a part of a multipart composition comprising a core-shell latex copolymer (a1) may further contain water such that the part provides at least a portion of the water in the multipart composition. The core-shell latex copolymer of component (a1) is water-dilutable, and this property can provide flexibility for the operator when applying the coating composition, for example, in a vehicle refinishing operation. However, this does not prevent the addition of supplemental water to the composition while the core-shell latex copolymer (a1) and the polyhydrazide compound (b1) are combined or afterward. The addition of this supplemental water may help reduce the viscosity of the composition, which may be useful in certain methods of applying the composition to a substrate, such as spraying, as described below.

[0030] Binder A) Binder a) of the aqueous composition comprises (a1) a core-shell latex copolymer having a pendant carbonyl group. In certain embodiments, binder a) of the coating composition further comprises at least one (co)polymer that is different from the core-shell latex copolymer (a1) but is reactive to polyhydrazide compounds present in the composition. (a1) Core-shell latex copolymer The aqueous composition comprises a core-shell latex copolymer having a carbonyl group. The composition may contain, for example, about 5 to about 50% by mass, or about 10 to about 50% by mass, of the core-shell latex copolymer (a1), based on the mass of the composition. In certain important embodiments, the core-shell latex copolymer should be included in the composition in an amount of about 15 to about 45% by mass, or about 20 to about 45% by mass, based on the total mass of the composition. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0031] As used herein, the term “core-shell latex copolymer” refers to a latex copolymer produced by a stepwise polymerization process having at least two polymerization steps. In one step, an emulsion polymerization process is carried out to produce a “core” copolymer. In another step, an emulsion polymerization process is carried out to form a “shell” polymer. In one embodiment, the core copolymer is synthesized in a free radical emulsion polymerization step that precedes the step of synthesizing the shell copolymer by free radical emulsion polymerization. The shell copolymer is typically formed in the presence of particles of the core copolymer in these embodiments. In another embodiment, typically, if the core copolymer is more hydrophobic than the shell copolymer, the free radical emulsion polymerization step of the shell copolymer may precede the free radical emulsion polymerization step of the core copolymer. An exemplary process according to this latter embodiment is disclosed in U.S. Patent No. 7,825,173, the disclosure of which is expressly incorporated herein by reference in whole. There is a period between the core formation stage and the shell formation stage during which no detectable polymerization occurs. However, this does not preclude the possibility of one or more additional polymerization steps being performed on the core formation and shell formation stages. Exemplary additional polymerization steps may be performed before the core polymer formation stage, between the core polymerization stage and the shell polymerization stage, or after the shell polymerization stage.

[0032] The shell formed by the shell copolymer should at least partially, and typically completely, cover the surface of the core copolymer. The core copolymer and the shell copolymer are physically and / or chemically bonded to each other, and in some embodiments, there may be interpenetration of polymer chains within the core and shell of the latex copolymer. However, the core-shell copolymer latex should have relatively distinct changes in polymer structure or composition when moving outward from the center along the radius of the latex particle, resulting in a morphology having a relatively distinct core portion with a certain polymer composition and a relatively distinct shell portion with a different polymer composition. In important embodiments, a core-shell latex copolymer is exemplified in that the core copolymer constitutes at least about 10% by mass, e.g., about 10 to about 70% by mass, or about 10 to about 50% by mass, of the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein. Regardless of, or in addition to, the above-mentioned properties, core-shell latex copolymers should be exemplified in that the core polymer has a higher glass transition temperature (Tg) than the shell polymer. In certain embodiments, the core copolymer has a calculated glass transition temperature (Tg) of about 20 to about 80°C, for example, about 40 to about 80°C, or about 50 to about 80°C. g The shell copolymer has a glass transition temperature (T) calculated to be approximately -30°C to approximately 30°C, for example, approximately -30°C to approximately 15°C, or approximately -30°C to approximately 0°C. g ) has. In other embodiments, the calculated glass transition temperature of the core copolymer is at least about 20°C, or at least about 30°C, higher than the calculated glass transition temperature of the shell copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein.

[0033] Regardless of, or in addition to, the glass transition temperatures of the core copolymer and the shell copolymer, core-shell latex copolymers typically have a calculated glass transition temperature of approximately -20 to approximately 40°C, based on all monomer residues present. In the available literature, monomers are sometimes defined by their glass transition temperature, which more precisely represents the glass transition temperature of the homopolymer obtained from the homopolymerization of that monomer. The monomers for each step in a series of polymerization steps are selected based on the glass transition temperature of the monomers so that the polymers at each step and the core-shell latex copolymer as a whole obtain the glass transition temperature according to the desired calculations. In one embodiment, although not intended to be mutually exclusive with the glass transition temperature characteristics described above, the core-shell latex copolymer may be exemplified by a minimum film formation temperature of less than about 45°C, for example, less than about 40°C, less than about 35°C, or less than about 30°C. The core-shell latex copolymer of the composition is typically measured by laser diffraction to have an average volume particle size (d) of about 10 nm to about 1000 nm, for example, about 50 nm to about 500 nm, or about 50 nm to about 400 nm. v 50) has. In various non-limiting embodiments, all values ​​and ranges of values, including integers and decimals, and between them, are explicitly intended for use herein.

[0034] To be complete, this disclosure does not preclude the inclusion of two or more types of core-shell latex copolymer particles having different particle size distributions in the composition in order to provide a balance of the key properties of the resulting cured product, including shear strength, peel strength, and resin fracture toughness. As described above, carbonyl-functionalized core-shell latex copolymers comprise at least two copolymers and are synthesized in a series of free-radical emulsion copolymerization steps. The monomers in each step are selected to obtain the desired polymer properties of each step, and as a whole, at least one of the monomer mixture of reactants forming the core copolymer and the monomer mixture of reactants forming the shell copolymer comprises iv) at least one hydroxyl-functionalized ethylenically unsaturated monomer and v) at least one carbonyl-functionalized ethylenically unsaturated monomer.

[0035] The following lists candidate monomers for the synthesis of core-shell latex copolymers. The term "complete monomer mixture" refers to all monomers whose residues are present in the core-shell latex copolymer, and represents the sum of all monomers present at the polymerization stage in which the core-shell latex copolymer is obtained. The mass percentage that a given monomer component may occupy is given based on the total mass of monomer residues in the core-shell latex copolymer. Monomer component i) : Aliphatic (meth)acrylate monomer of formula MA The total monomer mixture is i) Formula MA: H2C=CG a CO2R a (MA) (In the formula, G a is hydrogen, halogen, or methyl, R a C1-C 18 Alkyl, C2-C 18 Heteroalkyl, C3-C 18 Cycloalkyl, C2-C8 heterocycloalkyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkoxyaryl, C7-C 18 Alkaline, or C7-C 18 (It is Aralkir) It contains at least one ethylenically unsaturated functional monomer represented by [the specified formula].

[0036] Monomer component i) may account for about 40 to about 95% by mass, or about 50 to about 90% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. In important embodiments, the total monomer mixture is given by formula MA1: H2C=CG a CO2Ra1 (MA1) (In the formula, G a is hydrogen, halogen, or methyl, R a1 C1-C 18 Alkyl, C2-C 18 Heteroalkyl, C3-C 18 (These are cycloalkyl, C2-C8 heterocycloalkyl, C2-C8 alkenyl, or C2-C8 alkynyl compounds.) It contains at least one ethylenically unsaturated functional monomer represented by [the specified formula]. In exemplary embodiments, the monomer of formula MA1 may constitute about 50 to about 100% by mass, or about 90 to about 100% by mass, of the total mass of the monomer of formula MA in the total monomer mixture. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein.

[0037] Typical monomers conforming to formula MA1 are G a However, it is hydrogen, halogen, or methyl, and R a1 However, C1-C 18 Alkyl, or C3-C 18 It is a cycloalkyl monomer. a A monomer in which the hydrogen atom is methyl may be used. Examples of (meth)acrylate monomers conforming to formula MA1 that can be used alone or in combination include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and 4-tert-butylcyclohexyl (meth)acrylate. Examples include isobornyl (meth)acrylate, norbornyl (meth)acrylate, dihydrodicyclopenta(pentan)dienyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monododecyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, trifluoroethyl (meth)acrylate, and perfluorooctyl (meth)acrylate.

[0038] The presence of aromatic (meth)acrylate monomers in the total monomer mixture is not prevented, and therefore the total monomer mixture is given by formula MA2: H2C=CG a CO2R a2 (MA2) (In the formula, G a is hydrogen, halogen, or methyl, R a2 C6-C 18 Aryl, C1-C9 heteroaryl, C7-C 18 Alkoxyaryl, C7-C 18 Alkaline, or C7-C 18 (It is Aralkir) It may contain at least one ethylenically unsaturated functional monomer represented by . Examples of (meth)acrylate monomers conforming to formula MA2 (which may be used alone or in combination) include, but are not limited to, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxypropyl (meth)acrylate. In exemplary embodiments, the monomer of formula MA2 may constitute about 0 to about 20% by mass, or about 0 to about 10% by mass, of the total mass of the monomers of formula MA in the total monomer mixture. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein.

[0039] Monomer component ii) : Vinyl aromatic monomer The total monomer mixture in which the core-shell latex copolymer is the reaction product may contain at least one vinyl aromatic monomer. Monomer component ii) may account for about 0 to about 50% by mass, for example, about 0 to about 30% by mass, about 0 to about 20% by mass, or about 0 to about 10% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. Suitable vinyl aromatic monomers include, in particular, those of formula (VA):

[0040] [ka] (In the formula, R 1 is H or C1-C4 alkyl, Each R 2 These are independently hydrogen or a C1-C4 alkyl group. Ar is an unsaturated phenyl or a phenyl substituted with 1 to 5 substituents, where each substituent is independently a halogen or a C1-C4 alkyl group. n is an integer between 0 and 4. Examples of things represented by this include: Typical monomers conforming to formula VA are R1 However, it is H or methyl, and each R 2 However, the monomer is independently H or methyl, Ar is an unsaturated phenyl or a phenyl substituted with 1 to 5 substituents, each substituent is independently a halogen or a C1-C4 alkyl, and n is 0 or 1. Furthermore, exemplary vinyl aromatic monomers conforming to formula (VA) (which may be used alone or in combination) include, but are not limited to, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, and 4-chlorostyrene.

[0041] Monomer component iii) Polyfunctional ethylenically unsaturated monomers In certain embodiments, the core-shell latex copolymer comprises residues of at least one monomer having at least two ethylenically unsaturated groups and a mass-average molecular weight (Mw) of up to 600 daltons. If such monomers are present, the core and / or shell copolymer includes a partially or substantially crosslinked network. The amount of such monomers should be selected such that the ability of the core-shell latex copolymer to swell is not excessively suppressed, depending on the degree of crosslinking. For example, monomer component iii) may occupy about 0 to about 5% by mass, e.g., about 0.1 to about 2.5% by mass, or about 0.5 to 2.5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. Here, it is typical that about 70 to about 100% by mass of the total mass of the monomer of component iii), for example, about 80 to about 100% by mass, or about 90 to about 100% by mass, is present in the monomer mixture in which the shell copolymer is the reaction product. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein.

[0042] Exemplary monomers of component iii) that can be used alone or in combination include conjugated dienes, e.g., butadiene and isoprene; allyl compounds, e.g., allyl (meth)acrylate, diallyl phthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate; polyallyl ethers of polyols, e.g., trimethylolpropane, pentaerythritol, and sucrose; poly(meth)acrylates of alkane polyols; poly(meth)acrylates of oxyalkane polyols; and poly(C2-C4)alkylene glycol di(meth)acrylates. For example, the compounds that have practical applications here include, either individually or in combination, 1,2-ethanediol dimethacrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2,2-dimethylpropane-1,3-diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,10-decanediol diacrylate, and tricyclodecanedimethanol di(meth)acrylate.

[0043] Further exemplary compounds having two (meth)acrylate groups include formula DA1: H2C=C(R m )-C(O)O-(R n O) p -O(O)CC(R m )=CH2(DA1) (In the formula, Each R m These are independently H or CH3, Each R n It is independently a C2-C4 alkene, p is an integer between 1 and 8. Examples of compounds conforming to the following criteria are listed. Each R m Each R is independently H or CH3, preferably H, and each Rn p is independently ethylene or propylene, and p is preferably an integer between 1 and 5, or between 2 and 4. Exemplary compounds conforming to formula DA1 that can be used alone or in combination include, but are not limited to, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate.

[0044] Examples of tri(meth)acrylate compounds with practical applications in monomer component iii) include tri(meth)acrylates of trivalent polyols. Tri(meth)acrylates of alkoxylated trivalent polyols, particularly tri(meth)acrylates of ethoxylated, propoxylated, and / or butoxylated trivalent polyols may be used. Examples of trifunctional (meth)acrylate compounds include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated glyceryl tri(meth)acrylate. In certain embodiments, trimethylolpropane triacrylate (TMPTA) and / or pentaerythritol triacrylate (PETIA) may be used. Further (meth)acrylate compounds that have practical applications in monomer component iii) include, but are not limited to, di(trimethylolpropane)tetraacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate (Di-TMPTTA), and dipentaerythritol pentaacrylate (Di-PEPA).

[0045] Monomer component iv) : Hydroxyl-functionalized ethylenically unsaturated monomer The total monomer mixture of which the core-shell latex copolymer is the reaction product may contain iv) at least one hydroxyl-functional ethylenically unsaturated monomer. Monomer component iv) may account for about 0 to about 15% by mass, for example about 0 to about 10% by mass, or about 1 to about 5% by mass, based on the total mass of the monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values and ranges of values, including integers and decimals, both those described above and between them, are expressly contemplated for use herein. The hydroxyl-functional ethylenically unsaturated monomer may be present in the monomer mixture of which the core copolymer is the reaction product, in the monomer mixture of which the shell copolymer is the reaction product, or in both of the monomer mixtures. In certain embodiments, the core copolymer contains about 70 to about 100% by mass, for example about 80 to about 100% by mass, or about 90 to about 100% by mass of the total mass of the monomer residues of iv) the hydroxyl-functional unsaturated monomer in the core-shell copolymer. In various non-limiting embodiments, all values and ranges of values, including integers and decimals, both those described above and between them, are expressly contemplated for use herein.

[0046] Suitable hydroxyl-functional ethylenically unsaturated monomers that can be utilized in the synthesis of the core-shell latex copolymer include hydroxyalkyl esters having a primary or secondary hydroxyl group, derived from α,β-monoethylenically unsaturated monocarboxylic acids. These include, for example, hydroxyalkyl esters derived from acrylic acid, methacrylic acid, crotonic acid, or isocrotonic acid. In certain embodiments, the total monomer mixture has the formula HMA: H2C=CG a CO2R h (HMA) (wherein G a is hydrogen, halogen, or methyl, and R h is C1-C 18 hydroxyalkyl). It may contain at least one hydroxyl (meth)acrylate monomer represented by Typical monomers conforming to formula HMA are G a is hydrogen, halogen, or methyl, and R h is C1-C 12 is a monomer that is hydroxyl. G a is hydrogen or methyl, and R h is a monomer that is C1-C6 hydroxyalkyl can also be used.

[0047] Examples of (meth)acrylate monomers conforming to formula HMA include, but are not limited to, hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate. In one embodiment, the total monomer mixture may contain at least one hydroxyl-functional adduct of a monoepoxy ester and an unsaturated carboxylic acid. Under a catalyst, a nucleophilic addition reaction between the monoepoxy ester and the acid occurs to form a hydroxyalkyl ester, and this ester product is then included in the monomer mixture to be polymerized. This acid-catalyzed ring-opening reaction conventionally requires a catalyst, and examples of the catalyst include, for example, tertiary amines, quaternary ammonium compounds, and transition metal compounds. The reactant monoepoxy esters are typically glycidyl esters derived from aliphatic saturated monocarboxylic acids having a tertiary or quaternary carbon atom at the alpha (α-) position. Representative reactant monoepoxy esters are glycidyl esters of saturated α,α-dialkylalkane monocarboxylic acids having 5 to 13 carbon atoms or 9 to 11 carbon atoms in the acid molecule. Exemplary reactant monoepoxy esters include versatic acid glycidyl ester, commercially available from Hexion as Cardura E10, pival acid glycidyl ester, commercially available from Hexion as Cardura E5, and reaction products of tertiary fatty acids with up to 12 carbon atoms and epichlorohydrin.

[0048] The acid-functional compound of the reactant may be an aliphatic unsaturated monocarboxylic acid, among which non-limiting examples include α,β-monoethylene unsaturated monocarboxylic acids, e.g., acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and isocrotonic acid; C1-C6 alkyl half-esters of α,β-monoethylene unsaturated dicarboxylic acids, e.g., fumaric acid and maleic acid; and C1-C6 alkyl esters of α,β-monoethylene unsaturated tricarboxylic acids having one free carboxylic acid group. Acrylic acid and / or methacrylic acid as the acid-functional compound of the reactant in various embodiments. Monomer component v) : Carbonyl-functionalized ethylenically unsaturated monomers The total monomer mixture in which the core-shell latex copolymer is the reaction product contains v) at least one carbonyl-functionalized ethylenically unsaturated monomer. Monomer component v) may account for about 1 to about 15% by mass, for example, about 1 to about 10% by mass, or about 1 to about 5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0049] As described above, at least one of the monomer mixtures in which the core copolymer is the reaction product and the monomer mixture in which the shell copolymer is the reaction product contains v) at least one carbonyl-functionalized ethylenically unsaturated monomer. Therefore, the carbonyl-functionalized ethylenically unsaturated monomer may be present in the monomer mixture in which the core copolymer is the reaction product, in the monomer mixture in which the shell copolymer is the reaction product, or in both of the monomer mixtures. Here, it is typical that about 70 to about 100% by mass of the total mass of the monomer of component v), for example, about 80 to about 100% by mass, or about 90 to about 100% by mass, is present in the monomer mixture in which the shell copolymer is the reaction product. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein. Examples of carbonyl-functionalized ethylenically unsaturated monomers that may be useful here, either alone or in combination, include acrolein; methcrolein; 4-vinyl-benzaldehyde (p-formylstyrene); diacetone acrylamide; diacetone methacrylamide; diacetone acrylate; diacetone methacrylate; allyl acetone acetate; vinyl acetone acetate; vinyl acetone amide; acetoacetoxy(C1-C6) alkyl(meth)acrylates, e.g., acetoacetoxymethyl(meth)acrylate, 2-(acetoacetoxy)ethyl(meth)acrylate, 2-acetoacetoxypropyl(meth)acrylate; butanediol-1,4-acrylate-acetylacetate; and vinyl(C1-C6) alkyl ketones, e.g., vinyl methyl ketone, vinyl ethyl ketone, and vinyl isobutyl ketone. Diacetone acrylamide may be used in certain embodiments.

[0050] Monomer component vi) Monomers of formulas U1 and CU1 The total monomer mixture in which the core-shell latex copolymer is the reaction product may include vi) a monomer of formula U1, a monomer of formula CU1, and at least one monomer selected from mixtures thereof:

[0051] [ka] (In the formula, X is either O or S, A is a C2-C3 alkylene, R u is the formula -(Alk-L) y -R x It is the basis of, R v and R w These are independently H or C1-C8 alkyl, y is either 0 or 1. Alk is a C2-C8 alkylene, L is either -O- or -NR z -and here, R z is H or C1-C8 alkyl, R x (These are 2-(2-carboxyacrylamide)ethyl, vinyl, allyl group, isopropenyl, acryloyl, methacryloyl, or 2-hydroxy-3-(allyloxy)propyl).

[0052] Monomer component vi) may comprise about 0 to about 15% by mass, for example, about 1 to about 10% by mass, or about 1 to about 5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. Monomers conforming to formula U1, or independently, monomers conforming to formula CU1, may be present in a monomer mixture in which a core copolymer is the reaction product, in a monomer mixture in which a shell copolymer is the reaction product, or in both of the above monomer mixtures. Typically, here, about 50 to about 90% by mass, e.g., about 55 to about 85% by mass, or about 60 to about 80% by mass, of the total mass of the monomer of component vi) is present in the monomer mixture in which the shell copolymer is the reaction product. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein. Typical monomers of formulas U1 and CU1 are monomers in which X is O, A is C2 alkylene, and Alk is C2-C6 alkylene. Exemplary monomers of formula CU1 that can be copolymerized alone or in combination include N-(meth)acryloylurea, N-vinylethyleneurea, N-vinyloxyethylethyleneurea, N-(2-acryloyloxyethyl)ethyleneurea, N-(2-methacryloyloxyethyl)ethyleneurea, N-(acrylamidomethyl)ethyleneurea, and N-(2-methacrylamidoethyl)ethyleneurea (MAEEU). The last monomer is commercially available from Solvay as Sipomer® WAM II.

[0053] Monomer component vii) : Ethylene-unsaturated acid functional monomer The total monomer mixture in which the core-shell latex copolymer is the reaction product may contain vii) at least one ethylenically unsaturated acid-functional monomer. Monomer component vii) may account for about 0.1 to about 15% by mass, for example, about 0.5 to about 15% by mass, about 0.5 to about 10% by mass, or about 1 to about 5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0054] In its use here, the term "ethylenically unsaturated acid-functional monomer" refers to a monomer that has a negative charge (-CO2) when it is in aqueous solution. - ) can be expressed, and this anionic monomer exhibits an ethylenically unsaturated monomer that is not an associated monomer as defined below. Ethylene-unsaturated acid functional monomers can be selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Suitable ethylenically unsaturated sulfonic acids include, for example, vinyl sulfonic acid, methallyl sulfonic acid, allyloxybenzene sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamidobutanesulfonic acid, and 2-acrylamido-2,4,4-trimethylpentanesulfonic acid. Suitable ethylenically unsaturated phosphonic acids include, for example, vinyl phosphonic acid, allyl phosphonic acid, N-(meth)acrylamidoalkylphosphonic acid, and (meth)acryloyloxyalkylphosphonic acid.

[0055] Exemplary ethylenically unsaturated carboxylic acids may be selected from α,β-monoethylenically unsaturated monocarboxylic acids, α,β-monoethylenically unsaturated dicarboxylic acids, C1-C6 alkyl half-esters of α,β-monoethylenically unsaturated dicarboxylic acids, α,β-monoethylenically unsaturated tricarboxylic acids, and C1-C6 alkyl esters of α,β-monoethylenically unsaturated tricarboxylic acids having at least one free carboxylic acid group, as well as mixtures thereof. In certain embodiments, the ethylenically unsaturated carboxylic acid may be selected from methacrylic acid, acrylic acid, 2-ethylacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, α-phenylacrylic acid, itaconic acid, maleic acid, aconitic acid, crotonic acid, fumaric acid, cinnamic acid, p-chlorocinnamic acid, and mixtures thereof. In one embodiment, the amount of strong acid monomer in the total monomer mixture may be limited. The total monomer mixture may be exemplified by comprising an ethylenically unsaturated acid functional monomer having a pKa of less than 4, determined in water at 20°C, in an amount of less than 0.5% by mass, for example, less than 0.3% by mass, less than 0.2% by mass, or less than 0.1% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. To be precise, such acid monomers should typically be used in the form of free acids, but this does not prevent the constituent acid groups of the monomer from being partially or completely neutralized with a suitable base, as long as neutralization does not impair their participation in copolymerization. Suitable counterions for acidic groups include ammonium ions (NH4). + ); Quaternary amines; alkali metal cations, especially Li + kaNa + , and K + ; and also include alkaline earth metal cations.

[0056] Monomer component viii) The surface adhesion of the copolymer derived therefrom can be improved by incorporating certain additional functional groups into (meth)acrylate monomers. Therefore, in one embodiment, the core-shell latex copolymer further comprises viiii) residues of at least one (meth)acrylate monomer having an anhydride, phosphate, or phosphonate functional group. For example, monomer component viiii) may occupy, for example, about 0 to about 10% by mass, or for example, about 1 to about 5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. Examples of phosphate or phosphonate-functional monomers include 2-monomethacryloxyethyl phosphate, bis(2-methacryloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, bis-(2-acryloyloxyethyl) phosphate, methyl-(2-methacryloyloxyethyl) phosphate, ethyl methacryloyloxyethyl phosphate, methyl acryloyloxyethyl phosphate, ethyl acryloyloxyethyl phosphate, 2-hydroxyethyl methacrylate phosphate, and 10-[(2-methylpropa-2-enoyl)oxy]decyl dihydrogen phosphate (10-methacryloyloxydecyl dihydrogen phosphate). 4-methacryloxyethyl trimellitic anhydride may also be used.

[0057] Monomer component ix) : Ethylene-unsaturated associated monomers The core-shell latex copolymer may further contain residues of at least one ethylenically unsaturated associative monomer, ix). Monomer component ix) may account for about 0 to about 10% by mass, for example, about 0 to about 5% by mass, based on the total mass of monomer residues in the core-shell latex copolymer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. The term "ethylenically unsaturated associative monomer" as used herein refers to an ethylenically unsaturated monomer having a hydrophilic segment and terminal hydrophobic functional groups. The hydrophilic segment functions as a spacer. When associative monomers are polymerized in an aqueous medium, the spacer positions the hydrophobic functional groups sufficiently far from the polymer backbone, enabling hydrophobic association. The spacer usually, though not always, contains a C2-C4 alkoxyate group, with ethoxylate (EO), propoxylate (PO), and butoxylate (BO) groups being examples.

[0058] An example of an ethylenically unsaturated associated monomer, which may be used individually or in combination here, is the general formula AM1: R 4 -C(H)=C(R 5 )-A-(R 6 O) [a] -R 7 (AM1) (In the formula, R 4 is H, methyl, CO2H, or CH2CO2H, R 5 is hydrogen, halogen, or methyl, A is -CH2C(O)O-, -C(O)O-, -O-, -CH2O-, -CH2C(O)N-, -C(O)N-, -CH2-, -OC(O)-, -HC(O)O-, -NHC(O)NH-, -C6H4(R 8 )-NH-C(O)-O-,-C6H4(R 8 )-NH-C(O)-NH-, Each R 6 These are independently C2-C4 alkylenes, [a] has values ​​from 5 to 100, R 7 C1-C 30 Alkyl, C3-C 18 Cycloalkyl, C2-C5 heterocycloalkyl, C2-C 20 Alkenyl, C2-C 12 Alkinyl, C6-C 18 Aryl, C7-C 24 Alkaline, or C7-C 24 It is Aralkir, R 8 (It is -CH2- or -(C)(CH3)2-) Examples include those that possess the following characteristics.

[0059] According to general formula AM1, -(R 6 O) a The part represents a polyoxyalkylene, which may be a homopolymer, random copolymer, or block copolymer of C2-C4 oxyalkylene units. Typical monomer conforming to formula AM1: R4 is H, methyl, CO2H, or CH2CO2H, and R 5 is hydrogen, halogen, or methyl, A is -CH2C(O)O- or -C(O)O-, and each R 6 These are independently C2-C4 alkylenes, and [a] has a value of 10-30, R 7 C6-C 30 Alkyl, C3-C 18 Cycloalkyl, C6-C 18 Aryl, C7-C 18 Alkaline, or C7-C 18 It is Aralkir.

[0060] Typical monomers conforming to formula AM1 are R 4 However, H, methyl, CO2H, or CH2CO2H, and R 5 However, A is hydrogen, halogen, or methyl, and A is -C(O)O-, and each R 6 However, independently, they are C2-C3 alkylenes, and [a] has a value of 10-30, R 7 C6-C 30 It is an alkyl monomer. Exemplary monomers conforming to formula AM1 that can be copolymerized alone or in combination include lauryl ethoxylate[a](meth)acrylate, cetyl ethoxylate[a](meth)acrylate, stearyl ethoxylate[a](meth)acrylate, behenyl ethoxylate[a](meth)acrylate, lauryl ethoxylate[a]itaconate, cetyl ethoxylate[a]itaconate, stearyl ethoxylate[a]itaconate, behenyl ethoxylate[a]itaconate, lauryl ethoxylate[a]maleate, cetyl ethoxylate[a]maleate, stearyl ethoxylate[a]maleate, and behenyl ethoxylate[a]maleate, where [a] represents the number of moles of ethoxylation and has a value of 10 to 30. In other words, each of the above may be described as an ethoxylated compound having a degree of ethoxylation with 10 to 30 moles of ethylene oxide. Parameter [a] may have values ​​of 15 to 30 or 15 to 25 in certain embodiments. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0061] Monomer component x) : Any further monomer The core-shell latex copolymer may further contain residues of ethylenically unsaturated monomers other than those described above. Exemplary further monomers include: (meth)acrylate-functionalized oligomers; nitrogen (N-)-functionalized ethylenically unsaturated monomers other than those of formulas U1 and CU1; silane-functionalized ethylenically unsaturated monomers, e.g., methacrylateoxypropyltri(C1-C5)alkoxysilane and vinyltri(C1-C5)alkoxysilane; acetoacetyl-functionalized unsaturated monomers, e.g., acetoacetoxyethyl methacrylate; alkenes, e.g., ethylene and propylene; naphthalene monomers, e.g., 1-allylnaphthalene, 2-allylnaphthalene, 1-vinylnaphthalene, and 2-vinylnaphthalene; vinyl esters; vinyl Examples of reactive surfactants include vinylidene halides; vinyl ethers; alkyl vinyl ketones; cycloalkyl vinyl ketones; divinyl glycols; divinylbenzenes; heterocyclic aliphatic vinyl compounds; and surfactants containing (meth)acryl-, allyl-, vinyl- and styryl- groups in the surfactant molecule. Examples of reactive surfactants include allyloxynonylphenol polyoxyethylene ether sulfate, polyoxyethylene styrene-phenyl ether ammonium sulfate, sulfonated 3-pentadecylphenyl acrylate, and vinylbenzyl (benyl) sulfosuccinate.

[0062] Suitable (meth)acrylate-functional oligomers may be selected from (meth)acrylate-functionalized polyurethanes, (meth)acrylate-functionalized polybutadienes, (meth)acrylic polyol (meth)acrylates, polyester (meth)acrylate oligomers, polyamide (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and mixtures thereof. The oligomer may have one or more acrylate and / or methacrylate groups bonded to the oligomer skeleton, and these (meth)acrylate functional groups may be terminal on the oligomer and / or distributed along the oligomer skeleton. In certain embodiments, the (meth)acrylate-functionalized oligomers that react as monomers in the derivation of core-shell latex copolymers, or each thereof, have two or more (meth)acrylate functional groups per molecule and / or have a mass-average molecular weight (Mw) of 300 to 1000 daltons. With respect to (N-)-functionalized ethylenically unsaturated monomers other than the monomers of formula U1 or CU1 described above, the nitrogen functionalizing group may be nitrile, urea, or thiourea, or it may have an imid, amide, or amino nitrogen atom.

[0063] Examples of nitrile monomers include, but are not limited to, acrylonitrile and methchloronitrile. Examples of maleimide monomers include, but are not limited to, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide. And, although not limited to exemplary (meth)acrylamides, acryloylmorpholine, diacetone (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nt.butyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-octyl (meth)acrylamide, Nt.octyl (meth)acrylamide, N-dodecyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-(hydroxymethyl)acrylamide, N-isobutoxymethylacrylamide, N-butoxymethylacrylamide, N,N-dimethyl (meth)acrylamide, N,N- Examples include diethyl(meth)acrylamide, N,N-propyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N,N-dihexyl(meth)acrylamide, N,N-dimethylaminomethylacrylamide, N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminohexylacrylamide, N,N-diethylaminomethylacrylamide, N,N-diethylaminoethylacrylamide, N,N-diethylaminopropylacrylamide, N,N-dimethylaminohexylacrylamide, N-hydroxymethyl(meth)acrylamide, acrylamide-2-methylpropanesulfonate, and N,N'-methylenebisacrylamide.

[0064] It is not forbidden for the core-shell latex copolymer a1) to contain a residue of at least one amino(meth)acrylate monomer. As used herein, the term "amino(meth)acrylate" refers to a derivative of methacrylic acid or acrylic acid having a primary, secondary, or tertiary amino group, the amino group may be part of a linear, branched, or cyclic aliphatic or aromatic group. Preferably, the at least one amino(meth)acrylate monomer should be a tertiary amino(meth)acrylate, for example, particularly N,N-dialkylaminoalkyl(meth)acrylate. Exemplary monomers include N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylate, and N,N-dimethylaminopropyl acrylate.

[0065] In further embodiments, the core-shell latex copolymer may further include residues of at least one vinyl monomer having a nitrogen heterocyclic structure, although these embodiments are not intended to be mutually exclusive with the embodiments described above. The exemplary heterocyclic structure may have either five or six members, or may include an oxygen atom in addition to nitrogen, and the five-membered or six-membered ring may represent, for example, a pyridine, pyrimidine, pyridazine, imidazoline, imidazole, oxazoline, oxazole, or morpholine ring. Examples of such rings, which may be used alone or in combination, include N-vinylcaprolactam (NVC), vinylmethyloxazolidinone (VMOX), N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, and N-vinylpyrrolidone. Exemplary vinyl esters that can be copolymerized in this disclosure include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl valerate, vinyl hexanoate, vinyl decanoate, vinyl 2,2,3,5-tetramethylhexanoate, vinyl 2,4-dimethyl-2-isopropylpentanoate, vinyl 2,5-dimethyl-2-ethylhexanoate, vinyl 2,2-dimethyloctanoate, vinyl 2,2-diethylhexanoate, vinyl laurate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and monomers from the VEOVA® series available from Hexion.

[0066] As described above, the keto-functional core-shell latex copolymers according to this disclosure comprise at least two copolymers and are synthesized in a series of free radical emulsion copolymerization steps. Without intending to limit this disclosure, conventional polymerization conditions include temperatures in the range of about 25 to about 100°C, for example, about 50 to about 100°C, or about 75 to about 100°C. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. Polymerization pressure is generally not important, and therefore the polymerization steps can be carried out below atmospheric pressure, at atmospheric pressure, or above atmospheric pressure. In addition to pressure, the polymerization steps may be carried out in the exclusion of oxygen if necessary, and the reaction vessel may be provided with inert, dry gaseous blankets of, for example, nitrogen, helium, and argon. Here, free radical polymerization is induced by at least one radical-generating initiator. Conventionally, the polymerization composition should contain at least one radical-generating initiator in about 0.1 to about 2% by mass, for example, about 0.1 to about 1% by mass, about 0.1 to about 0.8% by mass, or about 0.1 to about 0.5% by mass, based on the total mass of the polymerizable monomer. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0067] A first exemplary class of radical initiators includes inorganic peroxides, e.g., peroxydisulfates, particularly their ammonium or alkali metal salts; perborate tetrahydrates, particularly their ammonium or alkali metal salts; and carbonate peroxyhydrates, particularly their ammonium or alkali metal salts. A further exemplary class of radical initiators suitable for use herein is organic peroxides, e.g., organic peroxides selected from cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, and mixtures thereof. While certain peroxides (e.g., dialkyl peroxides) may be useful here, hydroperoxides constitute a class of initiators useful in this disclosure. Furthermore, hydrogen peroxide itself can be used, but more desirable polymerization initiators are organic hydroperoxides. For completeness, the definition of hydroperoxide includes materials such as organic peroxides or organic peresters that decompose or hydrolyze to form organic hydroperoxides in situ, and examples of such peroxides and peresters are cyclohexyl and hydroxycyclohexyl peroxides, and t-butyl perbenzoate, respectively.

[0068] In one embodiment of this disclosure, the radical generation initiator is given by the following formula: R p OOH (In the formula, R p (A carbon atom is an aliphatic or aromatic group containing up to 18 carbon atoms.) It comprises at least one hydroperoxide compound represented by . In one embodiment, R p C1-C 12 Alkyl, C6-C 18 Aryl, or C7-C 18 It is Aralkir. Exemplary peroxide initiators that can be used alone or in combination include cumene hydroperoxide (CHP), paramentane hydroperoxide, t-butyl hydroperoxide (TBH), t-butyl perbenzoate, t-butyl peroxypivalate, di-t-butyl peroxide, t-butyl peroxyacetate, t-butyl peroxy-2-hexanoate, t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide, benzoyl peroxide, and dibenzoyl peroxide. Examples include oxides, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexa-3-yne, and 4-methyl-2,2-di-t-butylperoxypentane.

[0069] Further exemplary classes of radical-generating initiators suitable for use herein are azo polymerization initiators, such as azonitriles, azoesters, azoamides, azoamidines, azoimidazolines, macroazo initiators, and azo polymerization initiators selected from mixtures thereof. Representative examples of suitable azo polymerization initiators include: 2,2'-azobis(2-methylbutyronitrile); 2,2'-azobis(isobutyronitrile); 2,2'-azobis(2,4-dimethylvaleronitrile); 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); 1,1'-azobis(cyclohexane-1-carbonnitrile); 4,4'-azobis(4-cyanovaleric acid); dimethyl2,2'-azobis(2-methylpropionate); 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; 2,2'-azobis(N-butyl-2-methylpropionamide); 2,2'-azobis[2-(2-imidazolin-2-yl)propionamide] Examples include 2,2'-azobis[2-(2-imidazolin-2-yl)propane]; 2,2'-azobis(2-methylpropionamidine)dihydrochloride; 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate; polymers using 4,4-azobis(4-cyanovaleric acid) and α,ω-bis(3-aminopropyl)polydimethylsiloxane (VPS-1001, available from Wako Pure Chemical Industries, Ltd.); and 4,4'-azobis(4-cyanopentanoic acid) polyethylene glycol polymer (VPE-0201, available from Wako Pure Chemical Industries, Ltd.).

[0070] A redox initiator is a combination of an oxidizing agent and a reducing agent, and may also be useful in this disclosure. Suitable oxidizing agents may be selected from cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, and mixtures thereof. Corresponding reducing agents may be selected from alkali metal sulfites; alkali metal bisulfites; alkali metal metabisulfites; formaldehyde sulfoxylates; alkali metal salts of aliphatic sulfinic acids; alkali metal hydrogen sulfides; salts of polyvalent metals, especially Co(II) salts and Fe(II) salts, e.g., iron(II) sulfate, iron(II) ammonium sulfate, or iron(II) phosphate; dihydroxymaleic acid; benzoin; ascorbic acid; reducing sugars, e.g., sorbose, glucose, fructose, and / or dihydroxyacetone; and mixtures thereof.

[0071] In addition to initiators, free radical emulsion polymerization can be carried out in the presence of chain transfer agents, which move free radicals, reduce the molecular weight of the resulting copolymer, and / or control chain growth during polymerization. If added, the chain transfer agent should constitute approximately 0.01 to approximately 1% by mass, based on the total mass of the polymerizable monomers. The amounts of polymerization initiators and any chain transfer agents present can be determinants of the number-average molecular weight of the copolymer, but the choice of solvent is also important. The emulsion polymerization reaction is carried out in an aqueous medium. While the monomer concentration in the emulsion can vary, the mass ratio of monomer to water is typically in the range of about 1:20 to about 2:1, for example, about 1:5 to about 2:1, or about 1:2 to about 1.5:1. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein.

[0072] The diluent for the aqueous medium may consist of water, but this does not prevent the aqueous medium from further containing one or more polar cosolvents. If present, such polar cosolvents should have a boiling point of at least about 20°C, for example, at least about 30°C, or at least about 40°C, measured at 1 atmospheric pressure (1.01325 bar). Examples of such polar cosolvents, which may be used alone or in combination, are, but are not limited to, C1-C8 alkanols, e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and isobutanol; acetonitrile; N,N-di(C1-C4) alkyl acylamides, e.g., N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); hexamethylphosphoramide; N-methylpyrrolidone; pyridine; esters, e.g., (C1-C8) alkylacetate Examples include ethoxydiglycol acetate, dimethyl glutarate, dimethyl maleate, dipropyl oxalate, ethyl lactate, benzyl benzoate, butyloctyl benzoate, and ethylhexyl benzoate; ketones, such as acetone, ethyl ketone, methyl ethyl ketone (2-butanone), and methyl isobutyl ketone; ethers, such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), and 1,2-dimethoxyethane; 1,3-dioxolane; dimethyl sulfoxide (DMSO); and dichloromethane (DCM).

[0073] A series of free radical emulsion polymerization steps are carried out in the presence of a surfactant. The surfactant can be added to the monomer mixture to form a preemulsification, or it can be added directly to the polymerization reactor during emulsion polymerization, or both modes of addition may be used. In one embodiment, each step of emulsion polymerization is carried out in the presence of a surfactant comprising about 0.01 to about 10% by mass, for example, about 0.1 to about 5% by mass, or about 0.1 to about 2.5% by mass, based on the total mass of the polymerizable monomers. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein. It should be noted that in free radical emulsion polymerization, reactive surfactants, non-reactive surfactants, or both reactive and non-reactive surfactants may be used. The term “reactive surfactant” is defined here as any surfactant whose molecule can form crosslinks with the polymer, copolymer, or itself, or with other molecules. Here, the inclusion of ethylenically unsaturated groups in the surfactant molecule (e.g., by (meth)acrylic, allyl, vinyl, or styryl groups) allows the surfactant to be covalently incorporated into the latex copolymer, thereby stabilizing the latex and reducing the tendency of the surfactant to migrate.

[0074] Regardless of reactivity, suitable surfactants include anionic, nonionic, amphoteric, and cationic surfactants, as well as mixtures thereof. More generally, anionic and nonionic surfactants, as well as mixtures thereof, can be used. Suitable anionic surfactants for promoting emulsion polymerization include, but are not limited to, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, (C6-C 18 ) Sodium alkylphenoxybenzene sulfonate, (C6-C 18 ) Alkylphenoxybenzene sulfonate disodium, (C6-C 18 Examples include disodium dialkylphenoxybenzenesulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butylnaphthalenesulfonate, disodium dodecyldiphenyl ethersulfonate, disodium n-octadecyl sulfosuccinate, and phosphate esters of branched alcohol ethoxylates.

[0075] Suitable nonionic surfactants for promoting emulsion polymerization include, but are not limited to, linear or branched alcohol ethoxylates; C8-C 12Examples include alkylphenol alkoxylates, such as octylphenol ethoxylate; and polyoxy(C2-C3) alkylene block copolymers. Further useful nonionic surfactants include C8-C polyoxyethylene glycols. 22 Fatty acid esters; mono- and diglycerides; sorbitan esters and ethoxylated sorbitan esters; C8-C 22 Examples include fatty acid glycol esters; block copolymers of ethylene oxide and propylene oxide having a hydrophobic-lipophilic balance (HLB) value greater than 12; ethoxylated octylphenol; and combinations thereof.

[0076] Examples of commercially available surfactants with practical applications here include: linear alcohol alkoxylates, e.g., polyethylene glycol ether of cetearyl alcohol (a mixture of cetyl alcohol and stearyl alcohol), available from BASF Corporation under the trademark names PLURAFAC® C-17, PLURAFAC® A-38, and PLURAFAC® A-39; polyoxyethylene-polyoxypropylene block copolymers, available from BASF Corporation under the trademark names PLURONIC® F127 and PLURONIC® L35; ethoxylated linear fatty alcohols, e.g., DISPONIL® A 5060 (Cognis), Ethal LA-23, and Ethal LA-50 (Ethox Chemicals); branched alkyl ethoxylates, e.g., GENAPOL® X 1005 (Clariant Corporation); and secondary C 12 -C 14Alcohol ethoxylates, e.g., TERGITOL® S15-30 and S15-40 (Dow Chemical Co.); ethoxylated octylphenol surfactants, e.g., TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887 and 897 (Rhodia, Inc.), ICONOL® OP 3070 and 4070 (BASF Corporation), and SYNPERONIC® OP 30 and 40 (Uniqema); reactive anionic surfactants, e.g., Hitenol AR, KH and BC available from Montello Inc.; Reactsurf 2490 available from Solvay; reactive nonionic surfactants, e.g., Noigen RN available from Montello Inc.; Sigma Examples include sodium vinyl sulfonate available from Aldrich, as well as block copolymers of ethylene oxide and propylene oxide, such as PLURONIC® L35 and F127 (BASF Corporation).

[0077] In certain embodiments, free radical polymerization may be carried out in the presence of additives known in the field of emulsion polymerization. Exemplary additives include polymer stabilizers, emulsifiers, buffers, chelating agents, inorganic electrolytes, biocides, defoamers, and pH adjusters. In certain embodiments, emulsion polymerization may be carried out in the presence of at least one polymer stabilizer, which is sometimes identified in the art as a protective colloid. For example, the polymer stabilizer may be used in an amount of about 0 to about 10% by mass, for example, about 0.01 to about 5% by mass, or about 0.01 to about 2% by mass, based on the total mass of the emulsion. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. Examples of synthetic polymer stabilizers include, but are not limited to, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, poly(meth)acrylamide, carboxylate-functionalized polymers, and polyalkyl vinyl ethers. Examples of water-soluble natural polymer stabilizers include, but are not limited to, gelatin, pectin, alginate, casein, and starch. Examples of modified natural polymers that have practical applications as polymer stabilizers include methylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and allyl-modified hydroxyethylcellulose. Mixtures of synthetic protective colloids and natural protective colloids, for example, a mixture of polyvinyl alcohol and casein, may also be used.

[0078] The emulsifier may be present in an amount of about 0 to about 10% by mass, for example, about 0.01 to about 5% by mass, or about 0.01 to about 2% by mass, based on the total mass of the emulsion. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein. Useful emulsifiers include ethoxylated C2 with 5-250 moles of ethoxylation (EO). 10 -C 22 These are fatty alcohols, examples of which include lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and behenyl alcohol ethoxylate. In particular, one or more of ceteth-20, ceteareth-20, steareth-20, and behenth-25 can be used.

[0079] The following describes an example of a two-step polymerization process. First, i) At least one (meth)acrylate monomer represented by formula MA, Optionally, ii) at least one vinyl aromatic monomer, Optionally, iii) at least one monomer having at least two (meth)acrylate groups and having a mass-average molecular weight (Mw) of up to 600 daltons, Optionally, iv) at least one carbonyl-functionalized ethylenically unsaturated monomer, and Optionally, vi) at least one ethylenically unsaturated acid functional monomer A monomer mixture containing, Chain transfer agent, A solution of surfactant in water and A core-step monomer composition containing the following: Add the mixture to the first container while mixing to prepare the monomer preemulsion. Processing aids may be added as desired.

[0080] The polymerization reactor is filled with the desired amount of water, additional surfactant, and optionally processing aids. The polymerization reactor is equipped with an attached inert gas inlet and supply pump, and the reactor contents are maintained in an inert atmosphere while being heated with mixing and stirring. The contents of the reactor are brought to the desired polymerization temperature and maintained under these conditions for approximately 0.5 to 3 hours. The seeding stage is carried out in a manner consistent with the addition of monomers and surfactants by the preemulsion described above. The desired amount of core-stage monomer preemulsion is supplied to the reactor over a period of approximately 0.5 to 2 hours, and the free radical initiator solution is supplied separately to the reactor contents in parallel with the core-stage monomer composition. During this time, the reaction temperature is controlled. After the desired amount of core monomer composition is added to the reactor, the supply is stopped, and optionally, an additional amount of free radical initiator may be added to the reactor. The resulting reaction mixture can be maintained at a temperature of about 45 to about 90°C for a sufficient period of time to complete or substantially complete the polymerization reaction and obtain a first-step core copolymer particle emulsion. If the core-step monomer composition contains an ethylenically unsaturated acid-functional monomer, a base may be added to the emulsion to neutralize the acidic groups of the core copolymer.

[0081] A shell-stage monomer composition containing a desired complement of the shell-stage monomer and, if desired, a crosslinking agent, along with the other components listed above in the case of a core-stage monomer composition, can be mixed in a separate container following the same procedure outlined for the formulation of the core-stage monomer composition. Alternatively, a crosslinking agent can be added to a first container containing the material remaining from the core-stage monomer composition and mixed by stirring to form the shell stage, i.e., the second-stage monomer composition. Additional shell-stage monomers can be added to the composition if desired. The shell stage monomer, or second stage monomer, is metered and supplied to the polymerization reactor at a constant rate and mixed with the core copolymer emulsion. Simultaneously with the supply of the shell stage monomer, a sufficient amount of free radical initiator solution is metered and supplied to the reaction mixture to restart polymerization, resulting in the polymerization of the shell stage monomer, or second stage monomer, in the presence of the core stage, or first stage copolymer. The polymerization temperature is maintained for about 0.5 to about 3 hours, or until polymerization is complete. Unreacted monomers can be eliminated by completing a monomer chase step, which, as is known in the field of emulsion polymerization, may involve the addition of more initiator or temperature control for a period of time to maintain the radical flux from initiator residues.

[0082] The presence of residual monomers in the reaction mixture can be monitored by gas chromatography (GC). Alternatively, or in addition, the progress of each step of the polymerization reaction may be monitored by particle size analysis or solids content analysis. Once the desired level of monomer conversion is achieved, the reactor contents are cooled and then, if applicable, partially or completely neutralized by adding an appropriate amount of base. Typically, product emulsions containing core-shell latex copolymers have a total copolymer solids content of about 10 to about 60% by mass, for example, about 10 to about 50% by mass, or about 10 to about 45% by mass. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. However, it should be recognized that the initially formed aqueous emulsion may be concentrated by distillation (under reduced pressure) of some of the water, any co-solvents present, and any unreacted starting materials. Complete distillation of such compounds is not prevented, as it allows for the isolation of the core-shell copolymer in dry powder form. The aqueous copolymer emulsion, the concentrated aqueous copolymer emulsion, or any dry powder obtained therefrom may be stored as soon as it is produced. The core-shell copolymer should be placed in a container with an airtight or moisture-tight seal, which should preferably be opaque to light irradiation.

[0083] Carbonyl functionalized cobinder In certain embodiments, the binder of the aqueous composition may further contain at least one (co)polymer (a2) which is different from the core-shell latex copolymer (a1) but is reactive to polyhydrazide compounds present in the composition. The aqueous composition may contain about 0 to about 20% by mass of (a2) the at least one (co)polymer based on the mass of the composition. Whether or not the (co)polymer (a2) is included is one determinant of the solids content of the aqueous composition. The mass ratio of the solids of component (a1) core-shell latex copolymer to the solids of component (a2) can be about 100:0 to about 100:35, for example, about 100:1 to about 100:20, or about 100:1 to about 100:10. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0084] (Co)polymer (a2) may be distinguished from core-shell latex copolymer (a1) by its morphology, which lacks a core-shell structure. Alternatively, or in addition, (co)polymer (a2) may be distinguished from core-shell latex copolymer (a1) by its constituent monomer residues. An exemplary (co)polymer (a2) may be a carbonyl-functionalized polymer selected from poly(meth)acrylates, polyamides, polyesters, polyethers, polyolefins, polyurethanes, or copolymers thereof. In certain embodiments, the composition comprises at least one cobinder selected from a poly(meth)acrylate having a pendant carbonyl group, a polyurethane having a pendant carbonyl group, a polyester having a pendant carbonyl group, and mixtures thereof.

[0085] B) Crosslinking agent The crosslinking agent of this composition comprises (b1) at least one polyhydrazide. The at least one polyhydrazide is included in the aqueous composition in an amount such that the molar ratio of hydrazide groups to carbonyl groups in the composition is about 5:1 to about 1:5. The composition may be exemplified by a molar ratio of hydrazide groups to carbonyl groups of about 3:1 to about 1:3, for example, about 2:1 to about 1:2. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. In addition to the molar ratios described above, aqueous compositions may be exemplified by containing about 5 to about 30% by mass of (b1) at least one polyhydrazide based on the mass of the composition. For example, the composition may contain about 5 to about 25% by mass, or about 5 to about 20% by mass of (b1) at least one polyhydrazide. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein. "Polyhydrazides" are defined by at least two formulas -C(=O)-NH-N(R h )(R i )(wherein, R h and R i These are independently H or C1-C 12 This refers to compounds having a hydrazide group (which is alkyl). Such hydrazide groups are usually larger groups, for example, those of the formula -LC(=O)NH-N(R h )(R i(In the formula, L is -O-, -NH-, C1-C) 18 Alkylene, C2-C 18 Alkenylene, C3-C 18 Cycloalkylene, or C6-C 18 It is part of a group of divalent linking groups selected from allylene. Apart from this point, in certain embodiments, polyhydrazides can be exemplified by having 2 to 5 hydrazide functional groups, for example, 2 to 4 hydrazide functional groups. The use of dihydrazide compounds can be particularly mentioned.

[0086] Polyhydrazides may be polymeric or nonpolymeric, and combinations thereof are also possible. Examples of nonpolymeric polyhydrazides include hydrazide derivatives of aliphatic, alicyclic, or aromatic polycarboxylic acids, which are obtained by the reaction of hydrazine with their respective polycarboxylic acids. According to key embodiments of this disclosure, component (b2) is formula (DH1) H2N-N(H)-C(O)-L 1 -C(O)-N(H)-NH2(DH1) (In the formula, L 1 is a covalent bond, C1-C 18 Alkylene, C2-C 18 Alkenylene, C3-C 18 Cycloalkylene, or C6-C 18 (A divalent linking group selected from arylene) It includes at least one dihydrazide having [a specific characteristic]. Exemplary dihydrazides conforming to formula DH1 include maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide (ADH), phthalic acid dihydrazide, terephthalic acid dihydrazide, glutaric acid dihydrazide, sebacate acid dihydrazide, cyclohexane-1,4-dicarbohydrazide, and azelaic acid dihydrazide. As suggested above, these dihydrazides can be obtained by the reaction of hydrazine with the corresponding dicarboxylic acid.

[0087] A polymer hydrazide is a polymer having at least two hydrazide groups, for example, two to five hydrazide groups. Exemplary polymer hydrazides may have a mass-average molecular weight (Mw) of about 1 to about 2000 kDa, for example, about 1 to about 1000 kDa, or about 1 to about 500 kDa. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. Polymer hydrazides can be obtained by reacting hydrazine (H2NNH2) or a derivative thereof with a polymer having a pendant anhydride group, an epoxide group, a carboxylic acid group, or an isocyanate group. The hydrazine reactant is of the formula H2N-N(R h )(R i )(wherein, R h and R i These are independently H or C1-C 12 It can be represented by (being alkyl). Exemplary polymers of reactants include, but are not limited to, isocyanate-functional polyurethanes and carboxylic acid-functional poly(alkyl(meth)acrylates), for example, carboxylic acid-functional poly(C1-C 12 Examples include alkyl (meth)acrylates. In certain embodiments, isocyanate-functional polyurethanes can be obtained by the reaction of a polyisocyanate with a polyol under conditions in which the -NCO group is stoichiometrically in excess of the active hydrogen atoms of the polyol. Exemplary reactant polyols may be selected from polyester polyols, polyether polyols, polycarbonate polyols, and mixtures thereof.

[0088] (c) Additives and auxiliary components Aqueous compositions typically further include adjuvants and additives that can impart improved properties to these compositions. For example, adjuvants and additives can impart one or more of the following: improved adhesion to the substrate, reduced corrosiveness to the substrate surface, improved elastic properties, improved elastic recovery, extended possible processing time, faster curing time, reduced residual tackiness, and improved leveling. Examples of such adjuvants and additives include adhesion promoters, corrosion inhibitors, catalysts, curing retarders, the surfactants mentioned above, wetting agents, plasticizers, stabilizers, reinforcing agents, rheology control agents, biocides, flame retardants, colorants, organic cosolvents, and non-reactive diluents. Such adjuvants and additives may be used in any desired combination and proportion, provided that they do not adversely affect the properties and essential characteristics of the composition. While some exceptions may exist, these adjuvants and additives should not, in total, constitute more than approximately 50% by mass of the total composition. Since this disclosure assumes the practicality of a multipart composition, it should be noted that auxiliary materials and additives containing reactive groups are placed in separate parts of the composition from the binder and crosslinking agents described above. Alternatively, these auxiliary materials and additives containing reactive groups may be blended together with a suitable binder part or crosslinking agent part to ensure their storage stability. Non-reactive auxiliary materials may be incorporated into any of the parts of the composition.

[0089] The addition of certain additives can enhance the adhesion of a coating composition to a particular substrate. In this regard, the compositions of this disclosure contain, based on the mass of the composition, 0 to 5% by mass, for example, 0.5 to 5% by mass, of morin (2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxy-4H-1-coumarone-4-ketone), 3,7-dihydroxy-2-naphthoic acid (3,7-dihydroxynaphthalene (naphthlene)-2-carboxylic acid), pyrogallol carboxylic acid (2,3,4-trihydroxybenzoic acid), 3,4-dihydroxy-benzeneguanidine-acetic acid, gallic acid (3,4,5-trihydroxybenzoic acid), para-aminosalicylic acid (4-amino-2-hydroxybenzoic acid, PAS), and flutter acid (flutter The additive may include at least one selected from (4,4'-methylene-bis(3-hydroxy-2-naphthoic acid)), citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), and mixtures thereof. Among these compounds, examples include the use (alone or in combination) of citric acid, gallic acid, or para-aminoacetyl acid (PAS).

[0090] In certain embodiments, the composition may contain at least one silane coupling agent in an amount of about 0 to about 5% by mass, for example, about 0.5 to about 5% by mass, based on the mass of the composition. Such a compound should typically have 1 to 3 hydrolyzable functional groups and can play a role in enhancing the adhesion of the curable composition to a given surface. More specifically, the hydrolyzable silane groups of the coupling agent can react with the surface to remove unwanted hydroxyl groups. The coupling agent may further contain non-hydrolyzable functional groups that can react with the film-forming polymer to chemically link the polymer and the surface. Suitable silane coupling agents include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, bis(γ-trimethoxysilylpropylamine), γ-ureidopropyl-trimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutylmethyl-dimethoxysilane, and N-ethyl-γ-aminoisobutyltrimethoxysilane; glycidoxyp Examples include methylentricoryalkoxysilanes, such as 3-glycidoxy-1-propyl-trimethoxysilane; (meth)acrylooxypolymethylenetricoryalkoxy(alkoy)silanes, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropyl-triisopropoxysilane; γ-methacrylamidopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; α-glycidoxypropylmethyldiethoxysilane; vinyl-tris-(2-methoxyethoxy)silane; and α-chloropropyl-trimethoxysilane.

[0091] The corrosion inhibitor may be included in the aqueous composition in an amount of up to about 5% by mass, based on the mass of the composition. When added, the composition typically contains about 0.1 to about 2% by mass, for example, about 0.1 to about 1% by mass of the corrosion inhibitor. Exemplary corrosion inhibitors that may be present in the composition alone or in combination include salts of alkali metals, alkaline earth metals, and transition metals, such as salts of titanium, chromium, and zinc. Examples include magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium phosphate, magnesium silicate, zinc oxide, zinc hydroxide, zinc carbonate, zinc phosphate, and zinc silicate. In certain embodiments, the reinforcing agent may be included in the aqueous composition in an amount of up to about 10% by mass, based on the mass of the composition. Exemplary reinforcing agents may be selected from epoxy elastomer adducts and reinforcing rubbers in the form of dispersed core-shell particles that do not have pendant reactive groups.

[0092] It will be understood that the aforementioned reaction between (a1) the core-shell latex copolymer and (b1) the polyhydrazide compound may, in some embodiments, provide all of the film-forming resins of an aqueous composition. Further provision of carbonyl-functionalized (co)polymers different from (a1) the core-shell latex copolymer in the composition is also conceivable. However, in certain embodiments, the composition may contain one or more supplementary film-forming resins in up to about 35% by mass, for example, up to about 30% by mass, or up to about 25% by mass, based on the solids content of the composition. Any such supplementary film-forming resins contained in the composition may be thermosetting or thermoplastic, but should be dispersible, emulsifiable, or soluble in water. Rheology control agents that may be included in this composition typically include fillers, thickeners, and combinations thereof. The total amount of rheology control agents in the composition should generally not exceed about 40% by mass based on the mass of the composition. For example, the composition may contain about 0 to about 35% by mass, or about 0 to about 40% by mass, of rheology control agents based on the mass of the composition.

[0093] Examples of thickening agents include, but are not limited to, clay-based thickeners, such as organic clay; polysaccharides, such as guar and xanthan gum; polyacrylates; and associative thickeners. In particular, examples of polysaccharide thickeners include cellulose or cellulose derivatives, such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose nanofibers, and cellulose nanocrystals. In general, there is no particular intention to limit the shape of the particles used as fillers, and needle-shaped, spherical, ellipsoidal, cylindrical, bead-like, cubic, and plate-like particles can be used alone or in combination. Furthermore, it is conceivable that aggregates of two or more particle types may be used. Similarly, there is no particular intention to limit the size of the particles used as fillers. However, such fillers have conventionally been measured by laser diffraction and have dimensions of 0.1 to 1500 μm, for example, 1 to 1250 μm. 50 The particle size is small. Examples of fillers include, but are not limited to, calcium carbonate, calcium oxide, calcium hydroxide (lime powder), precipitated and / or calcined silica, zeolite, bentonite, wollastonite, magnesium carbonate, diatomaceous earth, barium sulfate, aluminum oxide, aluminum silicate, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other pulverized minerals. Organic fillers, in particular wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, chaff, pulverized walnut shells, and other shredded fibers may also be used. Short fibers, such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar® fibers, or polyethylene fibers may also be added.

[0094] If present, calcined and / or precipitated silica is preferably 10-90 m 2 They should have a BET specific surface area of ​​1 / g. When used, they do not result in any additional increase in the viscosity of the composition according to this disclosure, but contribute to the reinforcement of the cured composition. Larger, more advantageous distances are 100-250m 2 It is also conceivable to use calcined and / or precipitated silica having a BET specific surface area of ​​1 / g as a filler. Due to the larger BET surface area, the effect of reinforcing the cured composition can be achieved using a smaller proportion of silica by mass. Hollow spheres having a mineral shell or a plastic shell are also suitable as fillers. These may be, for example, hollow glass spheres commercially available under the trademark name Glass Bubbles®. Plastic hollow spheres such as Expancel® or Dualite® can be used, as described in European Patent No. 0520426, and these plastic hollow spheres are made of inorganic or organic material and have a diameter of about 1 mm or less, typically about 500 μm or less.

[0095] Fillers that impart thixotropy to a composition can be typical for many applications. Such fillers are also described as rheological adjuvants and include, for example, hydrogenated castor oil, fatty acid amides, and expandable plastics, such as PVC. For the purposes of this disclosure, “plasticizer” means a substance that reduces the viscosity of a composition and thus promotes its processability. Here, the plasticizer may constitute up to about 10% by mass or up to about 5% by mass, based on the total mass of the composition, and is typically selected from diurethanes; monofunctional linear or branched C4-C16 alcohol ethers, e.g., Cetiol OE (available from BASF); esters of abietic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid, and citric acid; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of fatty acids having an OH group or epoxidized; glycolic acid esters; benzoic acid esters; phosphate esters; sulfonic acid esters; trimellitic acid esters; polyether plasticizers, e.g., end-capped polyethylene or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffin; and mixtures thereof. In principle, phthalate esters can be used as plasticizers, but it should be noted that this is not typical due to their potential toxicity.

[0096] For the purposes of this disclosure, “stabilizer” should be understood as an antioxidant, UV stabilizer, heat stabilizer, or hydrolysis stabilizer. Here, the stabilizer may constitute a maximum of about 10% by mass, or a maximum of about 5% by mass, based on the total mass of the composition. Examples of standard commercially available stabilizers suitable for use herein include sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; hindered amine light stabilizer (HALS) type amines; phosphorus; sulfur; and mixtures thereof. As used herein, the term “colorant” refers to any substance that imparts one or more of the following visual effects to a composition: color, opacity, or other properties. Visual effects that may be imparted to a composition by a colorant, in addition to or independently of color, include reflectivity, pearlescent luster, shine, texture, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, and goniochromism. The term “colorant” is intended to encompass organic pigments, inorganic pigments, dyes, and tints. More than one colorant may be included in a composition, and each added colorant may be added independently in any suitable form, including loose particles, dispersions, and solutions.

[0097] As described above, the composition is aqueous and therefore mainly contains water as a solvent or as a continuous phase in the dispersion. However, in certain embodiments, the composition may further contain organic cosolvents and / or non-reactive diluents, which are useful in that they can moderate the viscosity of the composition. Exemplary cosolvents and non-reactive diluents include, but are not limited to, aromatic solvents, e.g., xylene, toluene, and cumene; C1-C6 alkanols, e.g., methanol, ethanol, n-propanol, i-propanol, n-butanol, s-butanol, t-butanol, or n-pentanol; ether solvents, e.g., ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol di-n-butyryl Examples include ethers, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol di-n-butyl ether; petroleum fractions, e.g., naphtha and Solvesso® products (available from Exxon); acetates, including glycol ether acetates; propionates, e.g., ethyl 3-ethoxypropionate; isobutyrates, e.g., methyl isobutyrate, ethyl isobutyrate, isobutyl isobutyrate, and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate (Texanol); adipates; sebacates; phthalates; benzoates; organophosphate esters or sulfonic acid esters; and sulfonamides.

[0098] Co-solvents and non-reactive diluents typically constitute less than about 10% by mass, for example less than about 8% by mass, or less than about 5% by mass, based on the total mass of the composition. By at least partially eliminating these co-solvents and non-reactive diluents, aqueous compositions can have a volatile organic compound (VOC) content of up to about 420 g / l, for example up to about 360 g / l, for example up to about 300 g / l, or even up to about 240 g / l, as measured according to ISO 11890-2:2006. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are expressly intended for use herein.

[0099] Methods and Uses To prepare the curable compositions of this disclosure, their components should be mixed under sufficient shear force to obtain a homogeneous mixture. The one-part (1K) composition thus assembled can demonstrate storage stability in that, while curable, the polyhydrazide compound remains unreacted until exposed to certain conditions, such as an increase in pH caused by the evaporation of amines from the composition. In the case of the aforementioned multi-part curable compositions of certain embodiments of this disclosure, the reactive parts (and optionally a diluent, e.g., water) are mixed together in a manner that induces their hardening. This mixing is considered to be achievable without the use of special conditions or equipment. Suitable mixing devices include static mixing devices; magnetic stirring bar devices; wire whisk devices; stick mixing devices, e.g., wooden tongue depressors; augers; batch mixers; planetary mixers; CWBrabender or Banburry® type mixers; and high-shear mixers, e.g., blade blenders and rotary impellers. When mixed, aqueous compositions conventionally contain about 10 to about 70% by mass, e.g., about 20 to about 70% by mass, or about 30 to about 60% by mass, based on the mass of the composition. Alternatively, but not mutually exclusive, the composition may be defined by a viscosity of about 0.05 to about 2 Pa.s, e.g., about 0.05 to about 1.5 Pa.s, or about 0.05 to about 1 Pa.s, measured using a Brookfield viscometer at about 25°C immediately after mixing of all its components. The term “immediately” should be interpreted as a period not exceeding 5 minutes. In various non-limiting embodiments, all values ​​and ranges of values, including those described above and between them, are expressly intended for use herein, whether integers or decimals.

[0100] There is no particular intention to limit the substrates to which this composition can be applied. In applications to vehicle panels, exemplary substrates may be metals, polymers, or combinations thereof. However, ferrous metals, e.g., iron, steel, and their alloys; non-ferrous metals, e.g., aluminum, zinc, and their alloys; and combinations thereof can be particularly mentioned. In the embodiments for illustrative purposes, the substrate may be formed from cold-rolled steel; electro-galvanized steel, e.g., hot-dip electro-galvanized steel, or electro-iron-zinc alloy plated steel; or aluminum. The above composition is applied to a material layer and then cured in situ. Prior to application of the composition, it is often recommended to pre-treat the relevant surface. Any such pre-treatment should include at least one of the following: cleaning the surface, polishing the surface, applying an anti-corrosion coating, or applying a conversion coating or conversion treatment thereto.

[0101] Cleaning serves to remove foreign matter from a surface. Cleaning processes are known in the art and can be carried out in single or multi-stage methods consisting of, for example, etching with an acid and optionally an oxidizing agent suitable for the substrate; ultrasonic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment, and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent, such as carbon tetrachloride or trichloroethylene; wiping the surface with a dry wipe; wiping the surface with a wet wipe moistened with a cleaning solution, such as an aqueous solution of phosphate; and rinsing with water, typically with deionized or demineralized water. In these examples where an aqueous alkaline degreasing bath is used, any remaining degreasing agent on the surface should be removed, typically by wiping and / or rinsing the substrate surface with deionized or demineralized water.

[0102] Considering the practicality of the composition as a primer in the automotive refinishing process, after such cleaning of the substrate surface, any defective areas may be sanded and the edges may be beveled to reduce the thickness of the existing surface finish and conform to the new finish. Both sanding and beveling may be performed, for example, using an orbital sander with sandpaper of a predetermined grit. After sanding, the defective areas may be cleaned again to remove any dust generated during the sanding operation, or any other subsequent dirt or foreign matter. The terms "chemical conversion coating" and "chemical conversion treatment" refer to surface treatments of a substrate that chemically convert the surface material into a different material. Typically, a metal or alloyed surface substrate for refinishing that has defect areas is chemically treated to provide a firmly bonded chemical conversion coating that consists of all or part of a stabilized form (e.g., an oxidized form) of the substrate metal. Such chemical conversion coatings can exhibit high corrosion resistance and provide strong bonding affinity to subsequent coating layers.

[0103] The compositions of the present disclosure are then typically applied to the surface of a pre-treated substrate by conventional application methods, such as brush coating; roll coating; knife coating; doctor blade application; printing; and spraying methods, including but not limited to air atomization spraying, air-assisted spraying, airless spraying, and high-volume low-pressure spraying. The composition is recommended to be applied to a surface with a wet film thickness of approximately 10 to 500 μm, for example, approximately 10 to 250 μm, or approximately 20 to 150 μm. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. Applying thin layers within a given range is more economical and reduces the possibility of harmful thick cured areas. However, excellent control must be exercised in the application of thin coatings or layers to avoid the formation of discontinuous cured films.

[0104] Curing of the compositions of this disclosure, when applied, typically occurs at temperatures within the range of about 20°C to about 120°C, for example, about 20°C to about 100°C, or about 20°C to about 80°C. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein. The preferred temperature depends on the specific compound present, as well as the desired drying and curing rate, and can be determined in individual cases by those skilled in the art, if necessary, using simple preliminary tests. Naturally, drying and curing at lower temperatures within the aforementioned ranges is advantageous because it eliminates the need to significantly heat or cool the mixture from the normally dominant ambient temperature. However, where applicable, the temperature of the mixture formed from each part of the composition may be raised above the mixing temperature and / or application temperature using conventional means, including microwave induction, ovens, or drying booths. The high temperature may be maintained for up to 60 minutes to ensure complete curing. The curing method of this disclosure may further include reducing the oxygen content in the environment of the curing material. This can be done by introducing nitrogen (N2) gas into the curing environment. However, this step is not necessary for the formation of a robust coating. The cured composition is typically supposed to fill in any defective areas and any further minor scratches on the surface of the substrate to which it is applied, thereby providing a smooth surface for applying subsequent coating layers. Furthermore, after application to the substrate surface and once fully cured, the cured composition may be sanded, for example, using an orbital sander with sandpaper of a predetermined grit. The sanded surface may be washed again to remove any dust generated during the sanding operation, or any other subsequent dirt or foreign matter.

[0105] The curable compositions of this disclosure are not prevented from being applied in multiple layers to obtain a curable composition of a desired coating thickness and to cover imperfections on a surface. In this situation, the applied curable composition coating may be at least partially cured prior to the application of subsequent coatings. For example, the applied curable composition coating may be subjected to a heat treatment that "flash off" at least some of the water components but does not fully cure the composition. Then, a further coating of the curable composition is applied on the partially cured coating, and the resulting article is subjected to curing conditions that fully cure both coatings. One embodiment of the present disclosure provides an article comprising a metal substrate and a multilayer coating disposed on the metal substrate, wherein at least one layer of the multilayer coating comprises a cured composition described herein. While the use of the cured composition as a solid color base coat, solid color top coat, and / or clear coat within such a multilayer coating is not precluded, the cured coating composition is more preferred in or as a primer layer.

[0106] An exemplary article is illustrated in Figure 1 attached herein. The illustrated article (1) comprises a metal substrate (10) and a multilayer coating (11) disposed on the metal substrate, the multilayer coating (11) comprising a primer layer (110) disposed on the metal substrate and containing a cured product of the composition, a base coat layer (120) disposed on the primer layer (110) and containing a compound that imparts color and / or visual effect, and a clear coat layer (130) disposed on the base coat layer (120). A primer layer (110) is typically applied to promote adhesion between the substrate surface and the subsequent coating layer. Furthermore, the primer coating layer can enhance the overall physical properties of the coating system, particularly its corrosion resistance and impact strength. Additionally, the primer coating layer can contribute to the overall appearance of the coating system by providing a smooth layer upon which subsequent layers can be applied. A primer layer (110), which may typically contain the cured product of the above composition, is depicted in Figure 1 as being placed in direct contact with the metal substrate (10). However, it will be understood that one or more intermediate coating layers may be placed between the metal substrate and the primer layer (110). A chemical conversion coating layer is a typical example of such an intermediate coating layer, which exhibits high corrosion resistance and can provide strong bonding affinity to the subsequent primer layer (110).

[0107] For illustrative purposes only, Figure 1 depicts a single primer layer (110). However, in certain embodiments, two or more primer layers (110) may be present. Whether the primers are applied in a single or multilayer manner, the total thickness of at least one primer layer can typically be about 10 to about 200 μm, e.g., about 10 to about 150 μm, about 10 to about 75 μm, or about 20 to about 75 μm. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above and between them, are explicitly intended for use herein. The base coat layer (120) in Figure 1 contains a compound that imparts color and / or visual effect and is placed on top of the primer layer (110). When the primer is applied in a multilayer manner, the base coat layer is placed on top of the uppermost primer layer relative to the surface of the metal substrate (10). For illustrative purposes only, Figure 1 depicts a single basecoat layer (120). However, in certain embodiments, two or more basecoat layers (120) may be present. The bottommost of these basecoat layers may be positioned in direct contact with the primer layer (110). Whether the basecoat is applied in a single or multilayer manner, the total thickness of at least one basecoat layer may typically be about 5 to about 100 μm, e.g., about 5 to about 50 μm, about 5 to about 40 μm, or about 5 to about 30 μm. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein.

[0108] In Figure 1, the clear coat layer (130) is positioned on top of the base coat layer (120). When the base coat is applied in a multilayer manner, the clear coat layer (130) is positioned on top of the outermost base coat layer relative to the surface of the metal substrate (10). The clear coat layer (130) typically has good chemical resistance, as well as resistance to mechanical wear and weathering. Furthermore, the clear coat layer (130) has excellent optical properties, including transparency and gloss. Again, for illustrative purposes only, Figure 1 depicts a single clear coat layer (130). However, in certain embodiments, two or more clear coat layers (130) may be present. The bottommost of these clear coat layers may be positioned in direct contact with the base coat layer (120). Whether the clear coat is applied in a single or multilayer manner, the total thickness of at least one clear coat layer can typically be about 10 to about 500 μm, e.g., about 10 to about 200 μm, about 20 to about 100 μm, or about 30 to about 90 μm. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are explicitly intended for use herein.

[0109] Each clear coat layer (130) of the article may, in certain embodiments, be at least substantially transparent to visible light. Thus, for example, each clear coat layer may have a transmittance (T) according to ASTM D1746 (2023). R ) Determined using measurements, it may be at least about 85%, at least about 90%, or at least about 95% transparent to visible light. Further exemplary articles are illustrated in Figure 2, which is attached herein. The illustrated article (1) comprises a metal substrate (20) and a multilayer coating (21) disposed on the metal substrate, the multilayer coating (21) comprising a primer layer (210) disposed on the metal substrate, the primer layer (210) comprising a cured product of the composition, a base coat layer (220) comprising a compound that imparts color and / or visual effect, disposed on the primer layer (210), a tie layer (225) disposed on the base coat layer (220), and a clear coat layer (230) disposed on the tie layer (225).

[0110] The tie layer (225) can be inserted between the base coat layer (220) and the clear coat layer (230) (which can enhance their adhesion). With this insertion, the tie layer (225) can typically be substantially transparent to visible light. Therefore, for example, the tie layer (225) has a transmittance (T) according to ASTM D1746 (2023). R ) Determined using measurements, it may be at least about 85%, at least about 90%, or at least about 95% transparent to visible light. For illustrative purposes only, Figure 2 depicts a single tie layer (225). However, in certain embodiments, two or more tie layers (225) may be present. In these embodiments, the bottommost of these tie layers may be placed in direct contact with the base coat layer (220), while the clear coat layer (230) containing the cured product of the composition will be placed in direct contact with the topmost of the tie layers (225). The total thickness of at least one tie layer may, in embodiments, be less than the total thickness of the clear coat layer (230). Alternatively, or in addition, the total thickness of at least one tie layer may be about 1 to about 50 μm, for example, about 1 to about 25 μm, about 5 to about 25 μm, or about 5 to about 20 μm. In various non-limiting embodiments, all values ​​and ranges of values, both integers and decimals, including those described above, and between them, are expressly intended for use herein.

[0111] The process for forming a multilayer coating conventionally includes the steps of i) preparing a metal substrate, ii) applying a first layer of a first coating composition in direct contact onto the metal substrate, iii) at least partially curing or at least partially drying the first layer, iv) applying a second layer of a second coating composition in direct contact onto the at least partially cured or at least partially dried first layer, v) at least partially curing or at least partially drying the second layer, vi) applying a third layer of a third coating composition in direct contact onto the at least partially cured or at least partially dried second layer, and vii) at least partially curing or at least partially drying the third layer. In an iterative process, steps vi) and vii) may be performed and repeated to place a fourth layer and further layers on the metal substrate. Considering the multilayer coatings illustrated in Figures 1 and 2, the first, second, third, and further compositions provide, as described above, at least one primer layer, at least one base coat layer, optionally at least one tie layer, and at least one clear coat layer.

[0112] The metal substrate prepared in step i) may typically be pre-treated prior to step ii). As described above, such pre-treatment may include at least one of the following: cleaning the surface of the metal substrate, polishing the surface of the metal substrate, applying an anticorrosion coating to the metal substrate, or applying a chemical conversion coating to the metal substrate. Regardless of cleaning the substrate, the surface of the metal substrate (10) may be polished. Polishing typically involves sanding, which can be performed, for example, using an orbital sander with sandpaper of a predetermined grit. After polishing the surface, the metal substrate may be cleaned to remove any dust generated during the polishing operation, or any other subsequent dirt or foreign matter. When used in the processes described, the term "at least partially cured" means that the curing of the curable coating composition has begun, and, for example, that crosslinking of the composition's components has begun. This term encompasses any degree of curing under the applied curing conditions, from the formation of a single crosslink to a fully crosslinked state. The rate at which a coating composition cures depends on a variety of factors, including its components, the functional groups of the components, and the parameters of the coating conditions.

[0113] The partial solidification of a given coating layer is generally an indicator of curing or drying. However, both drying and curing can also be indicated by other means, including, for example, a change in the viscosity of the coating layer, an increase in the temperature of the coating layer, and / or a change in the transparency / opacity of the coating layer. Steps iv) and vi) of the application process described above can typically be initiated only if the preceding layer, which is at least partially cured or partially dried, can substantially retain its shape when exposed to ambient conditions. "Substantially retaining its shape" means that at least about 50 volume%, more typically at least about 80 volume%, or about 90 volume%, of the at least partially cured or dried layer remains in shape and does not flow or deform when exposed to ambient conditions for a period of about 5 minutes. Under such circumstances, gravity may typically have little to no effect on the shape of the at least partially cured or partially dried layer when exposed to ambient conditions.

[0114] The shape of a layer that is at least partially dried or at least partially cured can typically affect whether the layer substantially retains its shape. For example, if a layer is rectangular or has another overly simple shape, a layer that is at least partially cured or dried may be more resistant to deformation than a layer with a more complex shape, even at a lower level of curing or a lower degree of dryness. In certain embodiments, the application of each subsequent layer (step iv); step vi)) is performed while the layer is still so-called “green” before the layer has reached its final cured state, at least partially cured or at least partially dried. In such embodiments, the application of the layers can be considered “wet-on-wet,” and adjacent layers may bond to each other at least physically and chemically. For example, the components of the first layer and each subsequent layer may be chemically crosslinked / cured along the application line, and the effect may be beneficial to the lifespan, durability, and appearance of the finished article. The distinction between partial curing and the final cured state is whether the partially cured layer can undergo further curing or crosslinking. This does not actually prevent functional groups from being present in the final cured state, but such groups may remain unreacted due to steric hindrance or other factors.

[0115] In the aforementioned iterative process, the thickness, width, shape, and continuity of each layer can be independently selected, and the preceding and succeeding layers may be the same or different from each other in one or more of these respects. For example, a given succeeding layer may contact only a portion of the exposed surface of at least a partially cured or dried preceding layer. Depending on the desired shape of the coating layer, the succeeding layer may be selectively constructed on top of the preceding layer. Various features and embodiments of this disclosure are described in the following examples, which are intended to be representative and not limiting. [Examples]

[0116] The following products and commercially available products are used in the examples. Sipomer WAM-II: N-(2-methacrylamidoethyl)ethyleneurea, available from Solvay. SR213: 1,4-Butanediol diacrylate, available from Arkema. VeoVa 10: Vinyl neodecanoate, available from Hexion Inc. Aerosol EF800: Monoester sulfosuccinate emulsifier, available from Solvay. Rhodacal DS-4: Anionic surfactant, available from Solvay. Surfynol 104H: Nonionic surfactant (75% by mass solution in ethyl glycol monobutyl ether), available from Evonik Industries. Hitenol BC 1025: Reactive surfactant (25% active), available from Montello Inc. Solsperse 27000: Alkylphenol ethoxylate-free (APE-free) polymer dispersant, available from Lubrizol. Dispersant 1: 106 mg KOH / g solids acid value of quaternary ammonium salt of polyacrylic acid; 35% by mass of dispersant in a 1:3 mixture of isopropyl alcohol and water. Dispersant 2: Quaternary ammonium salt of polyacrylic acid having an acid value of 44 mg KOH / g solids; 40% by mass of dispersant in water. ACD: Acrylic copolymer dispersion prepared according to Example 2 of European Patent No. 1784463. Bruggolite® FF6M: Disodium salt of 2-hydroxy-2-sulfonatoacetic acid, available from Brueggemann KG. The remaining ingredients mentioned below are available from Sigma Aldrich.

[0117] The following test methods were performed on coatings obtained from the compositions described below. viscosity The viscosity of the exemplary composition was measured at 25°C using a DIN4 Viscosity Flow Cup within 2 minutes of mixing all components of the composition. CRS panel preparationCold-rolled steel (CRS) panels were sanded with P180 sanding paper, then cleaned with PS4000 (available from Axalta) wipes, and dried before spraying with the composition to be evaluated. The sample to be tested was sprayed onto the panel and heated and dried at 60°C for 30 minutes. Wavescan Wavescans were performed using a Wavescan-DOI instrument available from BYK-Gardner GmbH, intended to simulate the visual impression of the resulting coating. This instrument provided a laser point source illuminating the sample at a 60° angle, and an accompanying detector measured the reflected light intensity at the same but opposite angles. Long-wave signals (structure size >0.6 mm) and short-wave signals (structure size <0.6 mm) were separated from the measured signals, respectively, using a mathematical filtering function. The meter was rolled along the surface, and the optical profile of the surface between the two ends of a given distance was measured point by point. The long-term waviness values ​​shown in the table below represent the variability of the long-wave signal amplitude and are normalized to a dimensionless value in the range of 0 to 100, where 0 represents the smallest variability (best) and 100 represents the largest variability (worst). Similarly, the short-term swell value represents the variability of the shortwave signal amplitude and is normalized to a unitless value within the range of 0 to 100, where 0 represents the smallest variability (best) and 100 represents the largest variability (worst).

[0118] Sanding characteristics The sanding grade of CRS panels was determined according to U.S. Federal Test Standard No. 141B-6321, documented in ASTM D3322-82 (2017), a standard method for testing primers and primer undercoats on pre-formed metals. Sanding may be performed under conditions of hand sanding, bare-down sanding, and full-panel sanding. Grades from 1 to 7 are given, with 7 being the highest performance grade and 1 being the lowest performance grade. Stone-throwing testThis test was performed using a gravureometer and Q-lab chilled cast iron grit 4-5 mm stones. The stones were placed in the gravureometer hopper, the air supply was powered on, and the air pressure was adjusted to 70 psi. The prepared CRS panel was placed in a dedicated holder, the instrument was powered on, and stones were impacted onto the panel for 10 seconds. The panel was then evaluated according to the ISO 20567 rating criteria.

[0119] Synthesis Example 1 and Comparative Synthesis Examples 1 and 2 Synthesis Example 1 (SE1), which provides an aqueous latex copolymer in accordance with this disclosure, and Comparative Synthesis Examples 1 and 2 (CSE1, CSE2), which provide aqueous latex copolymers not in accordance with this disclosure, were independently prepared according to the following procedure. For Synthesis Example 1 and Comparative Synthesis Examples 1 and 2, the calculated glass transition temperatures of the monomer mixes in Stage I and Stage II were identical. In a 5L four-necked round-bottom glass reactor equipped with a mechanical stirrer, thermocouple, condenser, and nitrogen purge, 637.3g of deionized (DI) water, 5.0g of sodium α-olefin sulfonate (emulsifier, 40% active), and 3.0g of sodium bicarbonate were added and heated to 79°C. The components listed in Table 1 below were added to the first Erlenmeyer flask and stirred to form a stable monomer preemulsification, which constituted the monomer mix for Stage I. Ammonium hydroxide was the last component added to the flask for pH adjustment. For SE1, CSE1, and CSE2, the calculated Tg of the monomer mix (intended to form the core of latex particles) was +69°C.

[0120] [Table 1]

[0121] The components listed in Table 2 below were added to the second Erlenmeyer flask and stirred to form a stable monomer preemulsion, which constituted the Stage II monomer mix. Ammonium hydroxide was the last component added to the flask for pH adjustment. For SE1, CSE1, and CSE2, the calculated Tg of the Stage II monomer mix was +0.7°C.

[0122] [Table 2]

[0123] The components listed in Table 3 below were added to a third Erlenmeyer flask and stirred to form a stable monomer preemulsification, which constituted the Stage III monomer mix. The molecular weight of this third stage shell was controlled through the use of 1-dodecanethiol as a chain transfer agent. [Table 3]

[0124] 81.0 g of monomer preemulsification prepared from the Stage II monomer mix (Table 2) and 24.1 ml of a 12.9% by mass aqueous solution of ammonium persulfate (APS) initiator were added to a reactor at 79°C to form a polymerization seed. After stirring at 100 rpm for 15 minutes at 79°C, an exothermic peak from the seeding reaction was observed, and the batch color changed from milky white to a bluish hue. Next, the delayed supply of the Stage I monomer preemulsification (Table 1) was started together with 204 ml of a 2.1% aqueous solution of ammonium persulfate (APS) initiator. The delayed supply of the Stage I (core) monomer emulsion was carried out over 50 minutes. 204 ml of initiator solution was added at a constant rate throughout the duration of the monomer emulsion supply.

[0125] Immediately after the monomer supply in Stage I was completed, the remaining monomer pre-emulsion (shell) in Stage II was started at a supply rate such that the monomer emulsion in Stage II would be completed in 130 minutes. During the monomer supply in Stage II, the supply of the initiator solution (2.1% aqueous ammonium persulfate (APS) solution) was continued. Immediately after the completion of the monomer supply in Stage II, the monomer mix in Stage III was supplied over a 3-minute duration. Subsequently, while stirring for 1 hour, the reactor was maintained at a temperature of 82 °C and then cooled to 65 °C for the purpose of adding the redox chase. The redox chase (20.3 ml of 14.7 mass% t-butyl hydroperoxide and 19.7 ml of 12.2 mass% Bruggolite® FF6M) was added in one shot at 5-minute intervals from each other for the purpose of reducing the residual monomer.

[0126] The properties of each latex produced are listed in Table 4 below.

Table 4

[0127] Synthesis Example 2 and Comparative Synthesis Example 3 For Synthesis Example 2 (SE2), which provides an aqueous latex copolymer according to the present disclosure, and Comparative Synthesis Example 3 (CSE3), which provides an aqueous latex copolymer not according to the present disclosure, the following procedures were independently followed. For Synthesis Example 2, the glass transition temperature calculated for the monomer mix in Stage I was 53 °C. For Comparative Synthesis Example 3, the glass transition temperature calculated for the monomer mix in Stage I was 53 °C. Into a mechanically stirred, thermocoupled, cooled, and nitrogen-purged 5 L four-neck round-bottom glass reactor, 365 g of deionized (DI) water, 1.6 g of sodium α-olefin sulfonate (emulsifier, 40% active), 1.5 g of sodium dodecylbenzenesulfonate, and 1.0 g of sodium bicarbonate were added and heated to 79 °C.

[0128] The components listed in Table 5 below were added to the first Erlenmeyer flask and stirred to form a stable monomer preemulsification, which constituted the monomer mix for Stage I. Ammonium hydroxide was the last component added to the flask for pH adjustment. [Table 5]

[0129] The components listed in Table 6 below were added to the second Erlenmeyer flask and stirred to form a stable monomer preemulsion, which constituted the Stage II monomer mix. Ammonium hydroxide was the last component added to the flask for pH adjustment. For Synthesis Example 2, the calculated glass transition temperature of the Stage II monomer mix was 0.3°C. For Comparative Synthesis Example 3, the calculated glass transition temperature of the Stage II monomer mix was -0.2°C.

[0130] [Table 6]

[0131] 45.0 g of monomer preemulsification prepared from the Stage II monomer mix (Table 6) and 24.1 ml of 12.9% by mass aqueous solution of ammonium persulfate (APS) initiator were added to a reactor at 79°C to form a polymerization seed. After stirring at 100 rpm for 15 minutes at 79°C, an exothermic peak from the seeding reaction was observed, and the batch color changed from milky white to a bluish hue. Next, the delayed supply of the Stage I monomer preemulsification (Table 5) was started together with 204 ml of 2.1% aqueous solution of ammonium persulfate (APS) initiator. The delayed supply of the Stage I (core) monomer emulsion was carried out over 50 minutes. 204 ml of initiator solution was added at a constant rate throughout the duration of the monomer emulsion supply. Immediately after the completion of Stage I monomer supply, the remaining Stage II monomer pre-emulsion (shell) was initiated at a supply rate that would complete the Stage II monomer emulsion in 130 minutes. The initiator solution (2.1% ammonium persulfate (APS) aqueous solution) was continuously supplied during the Stage II monomer supply.

[0132] Next, the reactor was kept at a temperature of 82°C while stirring for 1 hour, and then cooled to 65°C for the purpose of adding the redox chaser. The redox chasers (9.8 ml of 11.2% by mass of t-butyl hydroperoxide and 9.6 ml of 9.3% by mass of Bruggolite® FF6M) were added in single shots with a 5-minute interval between each to reduce residual monomers. The properties of the generated latex are listed in Table 7 below. [Table 7]

[0133] Preparation of the mill base: To form the mill base (hereafter MB1) contained in the two-part (2K) composition, the following components were ground together: 20 parts by mass of barium sulfate, 13 parts by mass of talcam, 18 parts by mass of aluminum silicate, 17 parts by mass of titanium dioxide, 4 parts by mass of dispersant 1, 8 parts by mass of dispersant 2, 1.4 parts by mass of heavy naphtha, 1 part by mass of pentanol, 0.1 parts by mass of aminomethylpropanol, 1.7 parts by mass of a 50% Surfynol 104 solution in ethylene glycol monobutyl ether, and 15.5 parts by mass of deionized water. Examples: Preliminary preparation of black dispersion: According to the components presented in Table 8 below, water, Solsperse 27000, surfactant solution, and aminomethylpropanol were added to a container and mixed for 15 minutes using an air mixer. While mixing using the air mixer, carbon black was added to the container, and after addition, mixing was continued for an additional 30 minutes. The resulting dispersion was milled using an LMZ mill and then filtered through a 10 μm filter.

[0134]

Table 8

[0135] A coating composition having the components listed in Table 9 below was prepared while mixing with a high-speed mixer-disperser operated at 1000 rpm. To promote the formation of a uniform dispersion, an aqueous latex and dihydrazide adipate were first mixed over a 10-minute duration, and then a mill base and the aforementioned black dispersion (Table 8) were added thereto and mixed for an additional 30 minutes. A blend of ethylene glycol ether acetate and epoxy silane was combined with the resulting mixture to form the final composition.

[0136]

Table 9

[0137] The results of the tests performed on the above coating composition are provided in Table 10 below.

[0138]

Table 10

[0139] The examples provided in this disclosure demonstrate excellent sanding ratings. Furthermore, the examples provided in this disclosure show low variability in both short-term and long-term swells, and good durability in stone chip resistance tests. It should be understood that various changes and modifications to the exemplary embodiments described herein will be obvious to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of this subject matter and without diminishing the intended benefits. Therefore, such changes and modifications are intended to be included within the appended claims. It should also be understood that the features of the dependent claims may be embodied in the respective compositions and methods of the independent claims.

[0140] Many modifications and other embodiments of the disclosure described herein will be recalled by those skilled in the art to the extent of this disclosure, provided that they benefit from the teachings provided in the foregoing. Therefore, it is understood that this disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims.

Claims

1. A water-based coating composition, Water and, a) A binder, (a1) A core-shell latex copolymer having a pendant carbonyl group, wherein the core-shell latex copolymer comprises a core copolymer and a shell copolymer disposed around the core copolymer, and each of the core copolymer and the shell copolymer is independent of each other. i) Formula MA: H 2 C=CG a CO 2 R a (MA) (In the formula, G a is hydrogen, halogen, or methyl, R a is C 1 -C 18 alkyl; C 2 -C 18 heteroalkyl; C 3 -C 18 cycloalkyl; C 2 -C 8 heterocycloalkyl; C 2 -C 8 alkenyl; C 2 -C 8 alkynyl; C 6 -C 18 aryl, C 1 -C 9 heteroaryl, C 7 -C 18 alkoxyaryl, C 7 -C 18 alkaryl, or C 7 -C 18 aralkyl) At least one (meth)acrylate monomer represented by, and Optionally, ii) at least one vinyl aromatic monomer, Optionally, iii) at least one monomer having at least two (meth)acrylate groups and having a mass-average molecular weight (Mw) of up to 600 daltons, and Optionally, iv) at least one hydroxyl-functionalized ethylenically unsaturated monomer It contains the residue, At least one of the core copolymer and the shell copolymer is v) comprising a residue of at least one carbonyl-functionalized ethylenically unsaturated monomer, A binder containing a core-shell latex copolymer, b) A crosslinking agent, (b1) Formula -C(=O)-NH-N(R h ) (Caution i ) (wherein, R h and R i H or C 1 -C 12 A polyhydrazide compound having at least two hydrazide groups (which are alkyl) Crosslinking agent containing Includes, The molar ratio of hydrazide groups to carbonyl groups in the composition is approximately 5:1 to approximately 1:

5. Coating composition.

2. Based on the total mass of the composition, Approximately 10 to 70% by mass of water, The core-shell latex copolymer having approximately 5 to approximately 50% by mass of (a1) pendant carbonyl groups, and Approximately 5 to approximately 30 mass%, (c) formula -C(=O)-NH-N(R h ) (Caution i ) (wherein, R h and R i H or C 1 -C 12 The at least one polyhydrazide compound having at least two hydrazide groups (which are alkyl) The coating composition according to claim 1, comprising:

3. The coating composition according to claim 1 or 2, wherein the molar ratio of hydrazide groups to carbonyl groups in the composition is about 3:1 to about 1:

3.

4. A coating composition according to any one of claims 1 to 3, having a maximum volatile organic compound (VOC) content of approximately 420 g / l as measured in accordance with ISO 11890-2:2006.

5. A coating composition according to any one of claims 1 to 4, having a minimum coating film formation temperature of less than approximately 30°C.

6. Glass transition temperature (T) calculated for core copolymers g c The temperature is approximately 20 to 80°C. Glass transition temperature (T) calculated for shell copolymers g s ) is approximately -30 to approximately 30°C, g c ga T g s The condition is that it is at least about 20°C higher than The coating composition according to any one of claims 1 to 5.

7. The core copolymer accounts for approximately 10 to approximately 70% by mass of the total mass of monomer residues in the core-shell latex copolymer. The shell copolymer accounts for approximately 90 to approximately 30% by mass of the total mass of monomer residues in the core-shell latex copolymer. The coating composition according to any one of claims 1 to 6.

8. Monomer component v) is acrolein; methacrolein; 4-vinyl-benzaldehyde; diacetone acrylamide; diacetone methacrylamide; diacetone acrylate; diacetone methacrylate; allyl acetate; vinyl acetate; vinyl acetateamide; acetoacetoxy (C 1 -C 6 ) Alkyl (meth)acrylate; butanediol-1,4-acrylate-acetylacetate; vinyl (C 1 -C 6 A coating composition according to any one of claims 1 to 7, comprising alkyl ketones and at least one monomer selected from mixtures thereof.

9. The coating composition according to claim 8, wherein monomer component v) contains diacetone acrylamide.

10. Core-shell latex copolymer vi) At least one monomer selected from the monomer of formula U1, the monomer of formula CU1, and mixtures thereof: 【Chemistry 1】 (In the formula, X is either O or S, A is C 2 -C 3 It is alkylene, R u The formula is -(Alk-L) y -R x It is the basis of, R v and R w H or C 1 -C 8 It is alkyl, y is either 0 or 1. Alk is C 2 -C 8 It is alkylene, L is -O- or -NR z - and here, R z is H or C 1 -C 8 It is alkyl, R x The coating composition according to any one of claims 1 to 9, further comprising a residue of 2-(2-carboxyacrylamide)ethyl, vinyl, allyl, isopropenyl, acryloyl, methacryloyl, or 2-hydroxy-3-(allyloxy)propyl.

11. In formula U1 or formula CU1, X is O, A is C 2 It is alkylene, Alk is C 2 -C 6 It is alkylene. The coating composition according to claim 10.

12. The coating composition according to claim 10, wherein monomer component vi) comprises at least one monomer selected from N-(meth)acryloylurea, N-vinylethyleneurea, N-vinyloxyethylethyleneurea, N-(2-acryloyloxyethyl)ethyleneurea, N-(2-methacryloyloxyethyl)ethyleneurea, N-(acrylamidomethyl)ethyleneurea, N-(2-methacrylamidoethyl)ethyleneurea (MAEEU), and mixtures thereof.

13. Core-shell latex copolymer vii) The coating composition according to any one of claims 1 to 12, further comprising a residue of at least one (meth)acrylate monomer having a phosphate or phosphonate functional group.

14. The coating composition according to claim 13, wherein monomer component vii) comprises at least one monomer selected from 2-monomethacryloxyethyl phosphate, bis(2-methacryloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, bis-(2-acryloyloxyethyl) phosphate, methyl-(2-methacryloyloxyethyl) phosphate, ethyl methacryloyloxyethyl phosphate, methyl acryloyloxyethyl phosphate, ethyl acryloyloxyethyl phosphate, 2-hydroxyethyl methacrylate phosphate, 10-[(2-methylpropa-2-enoyl)oxy]decyldihydrogen phosphate (10-methacryloyloxydecyldihydrogen phosphate), and mixtures thereof.

15. The coating composition according to any one of claims 1 to 14, wherein the binder further comprises at least one polymer having a pendant functional group that is different from (a2) core-shell latex copolymer (a1) and is reactive with a hydrazide group.

16. The coating composition according to claim 15, wherein the mass ratio of the solid content of component (a1) core-shell latex copolymer to the solid content of component (a2) is about 100:1 to about 100:

35.

17. The coating composition according to claim 15 or 16, wherein (a2) is selected from a poly(meth)acrylate having a pendant carbonyl group, a polyurethane having a pendant carbonyl group, a polyester having a pendant carbonyl group, and a mixture thereof.

18. (b1) is equation (DH1): H 2 N-N(H)-C(O)-L 1 -C(O)-N(H)-NH 2 (DH1) (In the formula, L 1 Covalent bond, C 1 -C 18 Alkylene, C 2 -C 18 Alkenylene, C 3 -C 18 Cycloalkylene, or C 6 -C 18 (A divalent linking group selected from arylene.) A coating composition according to any one of claims 1 to 17, comprising at least one dihydrazide having the following properties.

19. The coating composition according to claim 18, wherein (b1) comprises at least one dihydrazide selected from maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide (ADH), phthalic acid dihydrazide, terephthalic acid dihydrazide, glutaric acid dihydrazide, sebacate acid dihydrazide, cyclohexane-1,4-dicarbohydrazide, azelaic acid dihydrazide, and mixtures thereof.

20. A cured product obtained from the aqueous coating composition according to any one of claims 1 to 19.

21. Metal substrate and A multilayer coating placed on a metal substrate and An article comprising, wherein at least one layer of the multilayer coating comprises the cured product according to claim 20.

22. Multilayer coating, A primer layer comprising the curing product described in claim 20, which is disposed in direct contact with the substrate, A base coat layer comprising a compound that imparts color and / or visual effect, wherein the base coat layer is disposed in direct contact with the primer layer, A clear coat layer and a clear coat layer that are in direct contact with at least one base coat layer. The article according to claim 21, including the article described in claim 21.

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