Liquid or aerosol jet coating compositions for substrates, coated substrates and methods of coating

Abstract

A liquid-jet or aerosol-jet coating composition, applied to a metal substrate, and a method for coating a metal substrate.

Description

[Technical Field]

[0001] The present invention provides liquid spray or aerosol spray coating composition (specifically, substrate powder coating composition), coated substrate, articles including such coated substrates, and methods (method of coating a substrate and method of manufacturing an article or part thereof). [Previous Technology]

[0002] Coil coatings and extrusion coatings are often used economically for coating substrates. Such coatings are known to have many useful properties, such as abrasion resistance, flexibility, durability, corrosion resistance, weather resistance, crack resistance, and the like.

[0003] Roll-in coatings and extrusion coatings are used to impart durable and richly colored aesthetics in a wide range of applications, including metal building products. Extrusion coatings (also known as spray coatings) are applied by hand or electrostatically to preformed metal components, such as curtain walls, storefronts, windows, blinds, and the like, while roll-in coatings are applied by roller coating to flat metal sheets that are subsequently formed into building components, such as building panels, roofs, sidings, and the like.

[0004] A wide variety of liquid-applied coating compositions have been used to provide hardened coatings on the surfaces of various products, including, for example, metal building products. Hardened coatings preferably exhibit excellent substrate adhesion, prevent contamination and other coating defects (such as "popping," "blushing," and / or "blistering"), and maintain long-term resistance to degradation even when exposed to harsh environments. Furthermore, hardened coatings typically maintain suitable film integrity during manufacturing and can withstand the handling conditions that the substrate may experience during use.

[0005] Liquid-based coatings largely meet the needs of today's market, but they have some significant drawbacks associated with their use. Liquid coatings contain large amounts of water and / or organic solvents, which increases transportation costs. Therefore, when applying liquid coating compositions, a significant amount of energy (usually in the form of burning fossil fuels) must be consumed to remove water or solvents during the coating curing process. Once the organic solvents are expelled from the cured film, they result in the generation of volatile organic compounds (VOCs), or must be reduced by large, energy-intensive thermal oxidation processes. In addition, these processes can emit large amounts of carbon dioxide.

[0006] One known alternative to liquid coating is lamination. In this process, a laminated or extruded plastic film is bonded to a metal via a heating step. The products required to produce laminated films are compatible with only a limited number of thermoplastic materials (e.g., the material must have the tensile strength required to stretch into a film). The degree to which such films can be stretched is also limited, thus limiting the thickness of the final coating that can be applied to the substrate. Significant capital investment may also be required to upgrade existing production facilities to accept laminated steel or aluminum.

[0007] There is a need for an improved coating composition for rigid substrate applications that overcomes the aforementioned disadvantages associated with conventional liquid, powder, and laminate encapsulation coating compositions. [Summary of the Invention]

[0008] The present invention provides liquid spray or aerosol spray coating composition (specifically, substrate powder coating composition), coated substrate, articles including such coated substrates, and methods (method of coating a substrate and method of manufacturing an article or part thereof).

[0009] In one embodiment, a substrate liquid-jet or aerosol-jet coating composition is provided, comprising: polymer particles comprising a polymer with a number average molecular weight of at least 2000 Daltons, wherein the polymer particles have a particle size distribution with a D50 of less than 10 micrometers; and a liquid carrier comprising water comprising a major amount of the liquid carrier. A method for coating such a composition onto a metal substrate to form a coated metal substrate and a coated metal substrate are also provided. A method for using a coated metal substrate to form a metal package and a metal package are also provided.

[0010] In this document, "coil coating" composition refers to a coating composition suitable for direct application to rigid materials (unlike, for example, a freestanding plastic film, paper, or other fibrous material or metal foil at least 10 micrometers thick, which is applied (e.g., adhered) to the rigid material) or indirect application to a pretreatment layer or primer layer over a substrate, which is not derived from a freestanding film (i.e., a film formed prior to application to another substrate, such as by lamination). Therefore, by way of example, a powder coating composition applied to a paper layer over a metal substrate or applied to a laminated plastic layer over a metal substrate is not a coil coating composition as used herein.

[0011] "Liquid or aerosol jet coating composition" refers to a composition that includes polymer particles in a water-based carrier, thereby forming a water-based polymer dispersion.

[0012] The particle size mentioned herein can be determined by laser diffraction particle size analysis of starting materials (e.g., primary polymer particles, charge control agents, lubricants, etc.) using a Beckman Coulter LS 230 laser diffraction particle size analyzer or equivalent calibrated as recommended by the manufacturer.

[0013] In this context, "D-values" (D50, D90, D95, and D99) refer to the percentage of a sample volume that is divided into granularities when particles are configured in ascending order of granularity. For example, for a granularity distribution, the median is called D50 (or x50 when following certain ISO guidelines). D50 is a granularity in micrometers that divides the distribution into half larger than that diameter and half smaller than that diameter. Dv50 (or Dv0.5) is the median of a volume distribution. D90 describes a granularity where 90 percent of the distribution has a smaller granularity and 10 percent has a larger granularity. D95 describes a granularity where 95 percent of the distribution has a smaller granularity and 5 percent has a larger granularity. D99 describes a granularity where 99 percent of the distribution has a smaller granularity and 1 percent has a larger granularity. Unless otherwise specified herein, D50, D90, D95, and D99 refer to Dv50, Dv90, Dv95, and Dv99, respectively. The D values ​​specified herein can be determined by laser diffraction particle size analysis.

[0014] A "hardened" coating means a coating in which particles are covalently cured via a cross-linking reaction (e.g., a thermosetting coating) or simply fused to a continuous layer (e.g., a thermoplastic coating) without a cross-linking reaction, and adhere to a metal substrate, thereby forming a cured metal substrate. The term "hardened" does not imply anything related to the relative hardness or softness (Tg) of the coating.

[0015] "Adherent" coating refers to a hardened coating that adheres to a substrate (such as a metal substrate) according to the adhesion test described in the example section. An adhesion rating of 9 or 10, preferably 10, is considered adherent.

[0016] A "continuous" coating refers to a cured coating free from pinholes and other coating defects that would expose the substrate (i.e., areas of the substrate exposed through the cured coating). Such film defects / failures can be indicated by a current measured in milliamperes (mA) using the plate continuity test described in the use examples section. For the purposes of this application, when evaluated according to this test, a continuous coating would pass a current of less than 200 mA. A continuous coating can be a full-coverage coating that completely covers the substrate, or it can cover only a portion of the substrate, for example, as in a patterned coating.

[0017] A “patterned” coating (i.e., a multipart coating) means a hardened coating printed on two or more areas of a substrate surface, the substrate surface of which may or may not have “blank” areas between and / or around the printed (i.e., coated) areas, wherein the “blank” areas are not coated. A “patterned” coating means any coating having one or more of the following: (i) two or more hardened coating portions of the same chemical composition, which are not directly continuous, are disposed on different areas of the same substrate surface, and exist in the same overall multipart coating; (ii) two or more hardened coating portions of different chemical compositions (e.g., with different colors, gloss levels, etc.), which are disposed on different areas of the same substrate surface, and exist in the same overall multipart coating; or (iii) two or more hardened coating portions of the same chemical composition of different thicknesses or textures, which may or may not be directly continuous, may or may not be disposed on different areas of the same substrate surface, and may or may not exist in the same overall multipart coating. A patterned coating is distinct from a full-coverage coating. This also excludes: (a) a substrate coated only at the edges; (b) a substrate coated all but not at the edges; and (c) a coating that does not exhibit any of (i), (ii), or (iii). A patterned coating may include regular or irregular patterns of the coated area, which may be of various shapes (e.g., stripes, rhombuses, squares, circles, ovals). The terms "pattern" and "patterned" do not require any repetition of design elements, but such repetition may exist. The coated area of ​​the patterned coating is preferably "continuous" as defined above, because it is free of pinholes and other coating defects that would expose the substrate if the underlying coating were not present.

[0018] The term "substantially free" means that the composition or hardened coating of this disclosure contains less than 1,000 parts (ppm) of the stated component (if present). The term "essentially free" means that the composition or hardened coating of this disclosure contains less than 100 parts (ppm) of the stated component (if present). The term "essentially completely free" means that the composition or hardened coating of this disclosure contains less than 10 parts (ppm) of the stated component (if present). The term "completely free" means that the composition or hardened coating of this disclosure contains less than 20 parts (ppb) of the stated component (if present).

[0019] The term "bisphenol" refers to a polyphenolic compound having two phenyl groups, each comprising a six-carbon ring and a hydroxyl group attached to a carbon atom of that ring, wherein the two phenyl rings do not share any common atoms. For example, hydroquinone, resorcinol, catechol, and the like are not bisphenols because these phenolic compounds comprise only one phenyl ring.

[0020] When used in the context of a coating applied to a surface or substrate, the term "on" includes coatings applied directly (e.g., pure metal or pre-treated metal, such as electroplated steel) or indirectly (e.g., on a primer layer) to a surface or substrate. Thus, a coating, for example, applied to a pre-treated layer (e.g., formed from a chromium- or chromium-free pre-treated layer) or a primer layer overlying a substrate constitutes a coating applied to (or disposed on) a substrate.

[0021] The terms "polymer" and "polymeric material" include, but are not limited to, organic homopolymers, copolymers (such as, for example, block, graft, random, and alternating copolymers, trimers, etc.), and their blends and modifiers. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometric configurations of the material. Such configurations include, but are not limited to, symmetrical, antisymmetrical, and heterosymmetrical arrangements.

[0022] The term "aryl group" (e.g., aryl) refers to a closed aromatic ring or ring system, such as arylphenyl, arylnaphthyl, arylbiphenyl, arylfluorenylene, and indene, as well as heteroaryl (e.g., closed aromatic or quasi-aromatic cyclic hydrocarbons or ring systems, wherein one or more of the atoms in the ring are elements other than carbon (e.g., nitrogen, oxygen, sulfur, etc.)). Suitable heteroaryl groups include furanyl, thiophene, pyridyl, quinolinyl, isoquinolinyl, indole, isoindole, triazolyl, pyrrole, tetrazolyl, imidazolyl, pyrazolyl, azole, thiazolyl, benzofuranyl, benzobenzylthio, carbazole, benzozolyl, pyrimidinyl, benzimidazolyl, quinolinyl, benzothiazolyl, pyridyl, isozolyl, isothiazolyl, purinyl, quinazolyl, pyridyl, 1-oxidopyridyl, pyridyl, triazolyl, tetraazolyl, diazolyl, thiadiazolyl, etc. When such groups are divalent, they are usually called "extrinyl" or "heteroextrinyl" groups (e.g., furylene, pyridylene, etc.).

[0023] As used herein, the term "phenylene" refers to a six-carbon aryl ring (e.g., in a phenyl group) that may have any substituents (including, for example, halogens, hydrocarbon groups, oxygen atoms, hydroxyl groups, etc.). Thus, for example, the following aryl groups are each phenylene rings: –C6H4-, –C6H3(CH3)-, and –C6H(CH3)2Cl-. Additionally, for example, each of the aryl rings of a naphthyl group is a phenylene ring.

[0024] The terms "multiple" or "multi" refer to two or more of the items mentioned (e.g., materials, components, compositions, coating parts).

[0025] In the context of liquid or aerosol spray coating compositions, “different” means that the liquid or aerosol coating composition differs in one or more chemical / physical ways (e.g., monomer type / amount, molecular weight of polymer particles, color of coating composition, type / amount of additives) to provide one or more different functions (e.g., hardness, flexibility, corrosion resistance, aesthetics, tactile feel).

[0026] In this document, the term "comprise" and its variations are not limiting in the context of the description and embodiments. Such terms are to be understood as including the stated steps or elements, or groups of steps or elements, but not excluding any other steps or elements, or groups of steps or elements. "Consisting of" means, but is not limited to, anything following the phrase "consisting of". Thus, the phrase "consisting of" indicates that the listed elements are necessary or mandatory, and that other elements may be absent. "Consisting essentially of" means including any elements listed after the phrase, limited to other elements that do not interfere with or facilitate the activities or actions specified in this disclosure for the listed elements. Thus, the phrase "consisting essentially of" indicates that the listed elements are necessary or mandatory, but other elements are optional and may or may not be present, depending on whether they substantially affect the activities or actions of the listed elements. Any element or combination of elements described in this specification using open-ended language (e.g., comprise and its derivatives) may be regarded as otherwise described using closed-ended language (e.g., consist and its derivatives) and semi-closed-ended language (e.g., consist essentially and its derivatives).

[0027] The terms "preferred" and "preferably" are used to refer to embodiments in which the present disclosure may provide certain benefits in certain circumstances. However, other embodiments may also be preferred in the same or other circumstances. Furthermore, reference to one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present disclosure.

[0028] In this application, the terms such as “a,” “an,” and “the” are intended not only to refer to singular entities but also to include the overall category for which specific instances can be used as an explanation. The terms “a,” “an,” and “the” are used interchangeably with the term “at least one.” The phrases “at least one of” and “comprises at least one of” following the list refer to any one of the items in the list and any combination of two or more items in the list.

[0029] As used herein, unless otherwise expressly indicated in the text, the term "or" generally means its usual meaning, which includes "and / or". The term "and / or" means any one or all of the listed elements, or any combination of two or more of the listed elements.

[0030] Furthermore, throughout this document, all figures are assumed to be modified by the term "about" and, in some embodiments, preferably by the term "exactly." As used herein in connection with the quantity being measured, the term "about" refers to a variation in the quantity being measured that would be expected by someone skilled in the art to perform the measurement with a degree of care commensurate with the purpose of the measurement and the accuracy of the measuring equipment used. Throughout this document, "up to" a number (e.g., up to 50) includes that number (e.g., 50).

[0031] Also in this document, the range of numbers described by endpoints includes all numbers falling into that range as well as those with such endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.) and any subranges (e.g., 1 to 5 includes 1 to 4, 1 to 3, 2 to 4, etc.).

[0032] As used herein, the term "room temperature" refers to a temperature of 20°C to 25°C.

[0033] The terms “in the range” or “within a range” (and similar statements) include the endpoints of the range being stated.

[0034] Throughout this specification, references to "one embodiment," "an embodiment," "certain embodiments," or "some embodiments" refer to at least one embodiment of this disclosure that includes a specific feature, configuration, composition, or characteristic described in connection with that embodiment. Therefore, the appearance of such phrases throughout this specification does not necessarily refer to the same embodiment of this disclosure. Furthermore, specific features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

[0035] The above summary of this disclosure is not intended to describe each of the disclosed embodiments or every implementation thereof. The following more specific description illustrates illustrative embodiments. Throughout this application, guidance is provided by way of a list of examples, which may be used in various combinations. In various cases, the cited lists are merely representative groups and should not be construed as exclusive lists. Therefore, the scope of this disclosure should not be limited to the specific illustrative structures described herein, but extends at least to structures described by the language of those embodiments and their equivalent forms. Any element expressly described as a substitute in this specification may be expressly included in or excluded from the embodiments in any combination as desired. Although various theories and possible mechanisms may have been discussed herein, in no case should such discussion be used to limit the claimed subject matter.

Implementation Method

[0037] This disclosure provides liquid-jet or aerosol-jet coating compositions (i.e., coating compositions) (specifically, substrate liquid-jet or aerosol-jet coating compositions), coating of substrates, methods (e.g., methods for manufacturing a substrate liquid-jet or aerosol-jet coating composition, methods for coating a substrate, and methods for manufacturing a substrate), and articles including such substrates.

[0038] Examples of materials that can be coated herein may include, for example, metal articles, more preferably coil-coated metal sheets. Any metal may be used, such as aluminum, iron, copper, tin, steel, and the like. Aluminum and steel are preferred, with aluminum being particularly preferred. In some preferred embodiments, the substrate may comprise, for example, hot-dip galvanized metal.

[0039] Coated metals are high-performance materials used in a wide variety of applications, including, for example, metal building panels, metal roofs, sidings, garage doors, office furniture, household appliances, heating and cooling panels, automotive panels and components, and the like. In some preferred embodiments, the coated substrate can be used for curtain walls, windows, doors, panels, skylights, atrium systems, louvers, grilles, column canopies, and any kind of metal building components.

[0040] In one embodiment, this description provides a coated article, i.e., a substrate, preferably a metal substrate, wherein one or more coating compositions are applied to the coated article. In some coil-coated articles, a primer composition may be applied to the metal substrate before applying other coatings. Generally, the substrate is pretreated and then primed with a commercially available anti-corrosion coating. Various pretreatments and primers are known to those skilled in the art and may vary depending on the type of coating and the end use of the coating.

[0041] In some embodiments, a primer coating may be applied to the substrate prior to the application of other coatings. Generally, the substrate is pretreated and then primed with a commercially available anti-corrosion coating. Various pretreatments and primers are known to those skilled in the art and may vary depending on the coating type (roll-on or spray coating) and the end application of the coating. The primer coating (if used) preferably has a thickness of about 1 to 15 micrometers, more preferably 5 to 12 micrometers.

[0042] Therefore, preferably, the liquid-jet or aerosol-jet coating composition of the substrate disclosed herein, and preferably the cured coating, substantially does not contain any of bisphenol A, bisphenol F, and bisphenol S, or any structural units derived therefrom, or both; the liquid-jet or aerosol-jet coating composition of the substrate disclosed herein, and preferably the cured coating, substantially does not contain any of bisphenol A, bisphenol F, and bisphenol S, or any structural units derived therefrom, or both; the liquid-jet or aerosol-jet coating composition of the substrate disclosed herein, and preferably the cured coating, substantially completely does not contain any of bisphenol A, bisphenol F, and bisphenol S, or any structural units derived therefrom, or both; or the liquid-jet or aerosol-jet coating composition of the substrate disclosed herein, and preferably the cured coating, completely does not contain any of bisphenol A, bisphenol F, and bisphenol S, or any structural units derived therefrom, or both.

[0043] More preferably, the liquid-jet or aerosol-jet coating composition disclosed herein, and preferably the hardened coating, substantially contains no bisphenol compounds, structural units derived therefrom, or both; the liquid-jet or aerosol-jet coating composition disclosed herein, and preferably the hardened coating, substantially contains no bisphenol compounds, structural units derived therefrom, or both; the liquid-jet or aerosol-jet coating composition disclosed herein, and preferably the hardened coating, substantially completely contains no bisphenol compounds, structural units derived therefrom, or both; or, the liquid-jet or aerosol-jet coating composition disclosed herein, and preferably the hardened coating, completely contains no bisphenol compounds, structural units derived therefrom, or both.

[0044] Preferably, tetramethylbisphenol F (TMBPF) is not removed from the liquid-jet or aerosol-jet coating composition disclosed herein or from the hardened coating. TMBPF is 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol as described below, prepared by the following reaction:

[0045] In this context, "structural unit derived therefrom" refers to any submolecule component of a monomer or polymer that derives its structure from a reference molecule, which is the result of the reference molecule being used in its direct synthesis. Examples include aromatic propylene dioxide compounds (e.g., propylene dioxide ether of bisphenol (BADGE), propylene dioxide ether of bisphenol F (BFDGE)), and epoxy phenolic compounds. Furthermore, as used herein, this terminology does not include TMBPF (i.e., TMBPF is not derived from bisphenol F).

[0046] For example, the liquid-jet or aerosol-jet coating composition is substantially free of bisphenol A, and includes 600 ppm bisphenol A and 600 ppm bisphenol A propylene dioxide ether (BADGE), whether bisphenol A and BADGE are present in the composition in reacted or unreacted forms or in combination thereof.

[0047] The amount of bisphenol compounds (e.g., bisphenol A, bisphenol F, and bisphenol S) can be determined based on the starting material; given the small amount of such compounds, for convenience, a test method is not necessary, and parts per million (ppm) can be used instead of weight percentage.

[0048] Although the intentional addition of bisphenol compounds is usually undesirable, it should be understood that, due to factors such as environmental pollution of bisphenols, trace amounts of bisphenol may be present unintentionally in the composition or coating of this application.

[0049] Although the scientific evidence available to date suggests that trace amounts of these compounds that may be released from existing coatings do not pose any risk to human health, they are still considered by some to be potentially harmful to human health. Therefore, some people hope to eliminate these compounds from coatings on food contact surfaces.

[0050] In addition, it is desirable to avoid using components that are unsuitable for such surfaces due to factors such as taste, toxicity or other government regulatory requirements.

[0051] For example, in a preferred embodiment, the liquid-jet or aerosol-jet coating composition is "PVC-free". That is, the liquid-jet or aerosol-jet coating composition preferably contains (if present) less than 2% by weight of vinyl chloride material and other halogenated vinyl materials, more preferably less than 0.5% by weight of vinyl chloride material and other halogenated vinyl materials, and even more preferably less than 1 ppm of vinyl chloride material and other halogenated vinyl materials (if present).

[0052] As a general guideline to minimize potential issues such as toxicity, when tested according to the overall extraction test described in the example section, the hardened coating formed by the liquid-jet or aerosol-jet coating composition preferably includes (if it includes any detectable) less than 50 ppm, less than 25 ppm, less than 10 ppm, or less than 1 ppm of extractables. An example of such test conditions is exposing the hardened coating to a 10 wt% ethanol solution at 121°C, followed by exposure to the solution at 40°C for 10 days.

[0053] Such reduced total extractable values ​​can be achieved by limiting the amount of mobile or potentially mobile species in the cured coating. In this context, "mobility" refers to the material extracted from the cured coating based on the overall extractable test of the example section. This can be achieved, for example, by using pure rather than impure reactants, avoiding the use of hydrolyzable components or bonds, avoiding or limiting the use of low molecular weight additives that may not react efficiently to form a coating, and using optimized curing conditions optionally combined with one or more curing additives. This makes cured coatings formed from the liquid-jet or aerosol-jet coating compositions described herein particularly desirable for use on food contact surfaces. Liquid-jet or aerosol-jet coating compositions

[0054] According to this disclosure, a liquid-jet or aerosol-jet coating composition is provided. This coating composition refers to a composition comprising polymer particles in a water-based carrier, thereby forming a water-based polymer dispersion. In this document, "liquid-jet or aerosol-jet coating composition" is used interchangeably with "liquid or aerosol-jet coating composition," "liquid or aerosol coating composition," "coating composition," and "water-based polymer dispersion."

[0055] Such compositions can form a hardened adhesive coating on a substrate (such as a substrate). In particular, such compositions can also be applied to a coating substrate or portions thereof. Water-based polymer dispersions

[0056] The water-based dispersion forming the "liquid or aerosol spray coating composition" includes polymer particles in a water-based carrier. The water-based carrier includes water as the primary (i.e., main) liquid carrier. This means that the liquid carrier includes at least 51 wt% water. Although, preferably, inorganic solvents or other organic liquids are included in the liquid carrier, in some embodiments, less than 50 wt% of the liquid carrier is an organic liquid. Preferably, less than 25 wt%, more preferably less than 10 wt%, and even more preferably less than 1 wt% of the liquid carrier includes an organic solvent (e.g., an organic solvent such as ethanol).

[0057] The solid content of the coating composition (before being incorporated into the liquid jet or aerosol jet coating system) is preferably at least 10 wt%, at least 15 wt%, or at least 20 wt% by total weight.

[0058] The solid content of the coating composition (before being incorporated into the liquid jet or aerosol jet coating system) is preferably at most 50 wt%, at most 40 wt%, or at most 30 wt% by total weight.

[0059] The amount of polymer particles in the water-based carrier (i.e., the concentration of polymer particles in the coating composition) is preferably at least 30 wt%, at least 50 wt%, or at least 70 wt%, based on the total solids content of the coating composition (i.e., the total weight of the cured coating).

[0060] The amount of polymer particles in the water-based carrier (i.e., the concentration of polymer particles in the coating composition) is preferably at most 99 wt-%, at most 97 wt-%, or at most 95 wt-%, based on the total solids content of the coating composition (i.e., the total weight of the cured coating).

[0061] The preferred viscosity range of the liquid-jet or aerosol-jet coating composition (i.e., a water-based dispersion prior to undergoing a liquid-jet or aerosol-jet process) may vary for liquid-jet application versus aerosol-jet application. Viscosity may be measured by a Brinell viscometer according to ASTM 2196 (2020), Method A.

[0062] The viscosity of the coating composition used in the liquid jet application process is preferably at least 1 centipoise (cps), at least 10 cps, or at least 20 cps. The viscosity of the coating composition used in the liquid jet application process is preferably at most 50 centipoise (cps), at most 40 cps, or at most 30 cps.

[0063] The viscosity of the coating composition used in the aerosol spraying application process is preferably at least 1 centipoise (cps), at least 50 cps, or at least 100 cps. The viscosity of the coating composition used in the aerosol spraying application process is preferably at most 1,000 centipoise (cps), at most 500 cps, or at most 200 cps.

[0064] The preferred surface tension range of the liquid-jet or aerosol-jet coating composition (i.e., a water-based dispersion prior to undergoing a liquid-jet or aerosol-jet process) may vary depending on whether liquid-jet application is performed or aerosol-jet application is performed. Surface tension may be measured according to ASTM D1331 (2020), Method C.

[0065] The surface tension of the coating composition used in the liquid jet application process is preferably at least 10 millinewtons / meter (mN / m), at least 20 mN / m, or at least 30 nM / m. The surface tension of the coating composition used in the liquid jet application process is preferably at most 50 mN / m, at most 45 mN / m, or at most 40 mN / m.

[0066] The surface tension of the coating composition used in the aerosol spraying application process is preferably at least 10 millinewtons / meter (mN / m), at least 20 mN / m, or at least 30 nM / m. The surface tension of the coating composition used in the aerosol spraying application process is preferably at most 50 mN / m, at most 45 mN / m, or at most 40 mN / m.

[0067] The molecular weight of the polymer particles in the liquid-jet or aerosol-jet coating composition can be described by several key indicators, assuming that a general polymer covers a range of molecular weights. The number average molecular weight (Mn) is determined by dividing the total weight of the sample by the total number of molecules in the sample. The weight average molecular weight (Mw) is determined by multiplying the sum of all different molecular weights in the sample by the weight fraction of the sample at that molecular weight. The polydispersity index (Mw / Mn) is used to express the width of the molecular weight range of the sample. The higher the polydispersity index, the wider the molecular weight range. Mn, Mw, and Mw / Mn can all be determined by gel permeation chromatography (GPC) for different molecular weight polystyrene standards.

[0068] The Mn of the polymer particles in the water-based dispersion is at least 2,000 Daltons, more preferably at least 3,000 Daltons, and even more preferably at least 4,000 Daltons. The Mn of the polymer particles in the water-based dispersion can be in the millions (e.g., 10,000,000 Daltons), such as acrylic polymers that can be emulsion polymerized or certain other latex polymers that can be emulsion polymerized, but preferably Mn is at most 60,000 Daltons, more preferably at most 40,000 Daltons, and even more preferably at most 20,000 Daltons. Preferably, the Mn of the polymer particles in the water-based dispersion is at least 2,000 Daltons and at most 60,000 Daltons, more preferably at least 3,000 Daltons and at most 40,000 Daltons, and even more preferably at least 4,000 Daltons and at most 20,000 Daltons.

[0069] The polymer particles in the water-based dispersion can be made from polymers with a polydispersity index of less than 4, less than 3, less than 2, or less than 1.5. However, it may be advantageous for the polymer to have a polydispersity index outside the aforementioned range. For example, to avoid being bound by theory, it may be desirable to have a higher polydispersity index in order to achieve both higher molecular weight (e.g., for flexibility and other mechanical properties) and lower molecular weight (e.g., for flow and leveling) in the same material.

[0070] The polymer particles in the water-based dispersion preferably have a particle size distribution with a D50 (preferably, D90, D95, or D99) of less than 10 micrometers, less than 5 micrometers, or less than 0.5 micrometers. The polymer particles in the water-based dispersion preferably have a particle size distribution with a D50 (preferably, D90, D95, or D99) of at least 0.01 micrometers, at least 0.05 micrometers, or at least 0.1 micrometers.

[0071] A suitable method for determining the particle size of polymer particles in water-based dispersions and other starting materials (e.g., lubricants) is laser diffraction particle size analysis. An exemplary apparatus for this analysis is a Beckman Coulter LS 230 laser diffraction particle size analyzer or equivalent calibrated according to the manufacturer's recommendations. It is believed that the particle size analysis of this analyzer conforms to the principles of the international standard ISO 13320:2009(E).

[0072] Samples for laser diffraction particle size analysis can be prepared, for example, by diluting the sample in a substantially non-swelling solvent (such as cyclohexanone or 2-butoxyethanol) and shaking until uniformly dispersed. The choice of suitable solvent will depend on the specific particles being tested. Solvent screening tests may be required to identify suitable substantially non-swelling solvents. For example, a solvent in which the polymer particles swell by about 1% or less (as determined by laser diffraction particle size analysis) would be considered substantially non-swelling.

[0073] The polymer particles may include one or more thermoplastic polymers, one or more thermoset polymers, or any suitable combination thereof. For certain preferred applications, the polymer particles may include one or more thermoplastic polymers. The term "thermoplastic" refers to a material that melts and changes shape when sufficiently heated and hardens when sufficiently cooled. Such materials are generally able to withstand repeated melting and hardening without exhibiting significant chemical changes. In contrast, "thermoset" refers to a cross-linked material that does not "melt".

[0074] The polymeric material preferably has a melt flow index greater than 15 g / 10 min, greater than 50 g / 10 min, or greater than 100 g / 10 min. The polymeric material preferably has a melt flow index of up to 200 g / 10 min, or up to 150 g / 10 min. The melt flow index is measured at 190°C and 2.16 kg weight according to ASTM D1238-13 (2013).

[0075] In some embodiments, the polymer particles are made of semi-crystalline, crystalline, amorphous polymers, or combinations thereof. Suitable semi-crystalline or crystalline polymers may exhibit any suitable degree of crystallinity. In some embodiments, the liquid or aerosol coating composition disclosed herein includes at least one semi-crystalline or crystalline polymer with a percentage crystallinity (by volume) of at least 5%, at least 10%, or at least 20%. For example, the percentage of crystallinity of a given polymer can be evaluated by differential scanning calorimetry (DSC) testing using the following equation: Percentage of crystallinity (%) = [A / B] × 100 Where: "A" is the heat of fusion of the given polymer (i.e., the total area under the melt portion of the DSC curve), in joules per gram (J / g); and "B" is the heat of fusion of the polymer in its 100% crystalline state, in J / g.

[0076] For many polymers, theoretical B values ​​are available in the scientific literature and can be used. For polyester polymers, for example, if such B values ​​are not available in the literature, the B value of 145 kg can be used as an approximation, which is the heat of fusion of 100% crystalline polybutylene terephthalate (PBT), as described in Cheng, Stephen; Pan, Robert; and Wunderlich, Bernard; "Thermal analysis of poly(butylene terephthalate) for heat capacity, rigid-amorphous content, and transition behavior," Macromolecular Chemistry and Physics, Volume 189, Issue 10 (1988): 2443-2458.

[0077] Preferably, at least one polymer material in the polymer particles (and more preferably substantially all or all of the polymer material present in the polymer particles) is at least semi-crystalline (e.g., semi-crystalline or crystalline). The polymer particles may include amorphous polymer materials or blends of at least semi-crystalline polymer materials and amorphous polymer materials. ASTM-D3418-15 (2015) is an example of a useful method for evaluating the crystallinity characteristics (crystallization peak temperature) of polymers.

[0078] The polymer used may exhibit any suitable glass transition temperature (Tg) or combination of Tg. The polymer particles are preferably made of an amorphous polymer having a glass transition temperature (Tg) of at least 15°C, at least 20°C, or at least 25°C, and a Tg of at most 150°C, at most 125°C, at most 110°C, at most 100°C, at most 80°C, or at most 50°C.

[0079] Polymers with lower Tg (e.g., having a Tg below 15°C, such as having a Tg below 0°C) can be used to make polymer particles as used herein, provided that the particles include at least one polymer having a higher Tg (e.g., at least 15°C).

[0080] The polymer particles may additionally have a core-shell morphology (i.e., the outer portion or shell of the polymer particle is composed of a different component than the inner portion or core). In such cases, the shell ideally comprises 10% or more of the total polymer particles, and the above Tg preference will apply only to the shell of the polymer particle. In other words, the shell of the polymer particle is preferably made of a polymer with a Tg of at least 15°C, at least 20°C, or at least 25°C, and a Tg of at most 150°C, at most 125°C, at most 110°C, at most 100°C, at most 80°C, or at most 50°C.

[0081] The polymer particles are preferably made of a crystalline or semi-crystalline polymer having a melting point of at least 40°C and at most 130°C.

[0082] In a preferred embodiment, substantially all (i.e., more than 50 wt%) of the polymer material of the polymer particles exhibits such a melting point or Tg. Classical amorphous polymers do not, for example, exhibit any identifiable melting point (e.g., do not exhibit a DSC melting peak) nor do they include any crystalline regions. Therefore, such classical amorphous polymers would be expected to exhibit a crystallinity percentage of 0%. Therefore, the liquid-jet and aerosol-jet coating compositions disclosed herein may include one or more amorphous polymers with a crystallinity of 0% or substantially 0%. However, if desired, the liquid-jet and aerosol-jet coating compositions disclosed herein may include one or more "amorphous" polymers with a crystallinity not of 0 (e.g., less than 5%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, etc.).

[0083] The one or more polymers in the polymer particles may be aliphatic or aromatic, or a combination of one or more aliphatic polymers and one or more aromatic polymers. Similarly, the one or more polymers may be saturated or unsaturated, or a combination of one or more saturated polymers and one or more unsaturated polymers.

[0084] Suitable polymer particles can be prepared from water (e.g., latex polymers) or from organic solvents (e.g., nonane, decane, dodecane, or isohexadecane) or combinations thereof. Due to cost considerations, water-based polymers are preferred to maintain low VOC content during processing and to keep residual organic solvents away from the liquid or aerosol coating composition.

[0085] The polymer particles may be polymer particles produced by emulsion, suspension, solution, or dispersion polymerization (i.e., particles produced by emulsion, suspension, solution, or dispersion polymerization processes). Generally, such polymers include self-emulsifying groups (e.g., carboxylic acids, sulfonic acids, phosphine groups, or salts thereof), but this is not essential. Neutralizing agents (e.g., amines, ammonia, or ammonium hydroxide), especially volatile ones, may also be used to manufacture such polymer particles, as is well known to those skilled in the art. Conversely, bases for acid neutralization may also be used if desired. Nonionic polar groups may also be used alternatively or additionally.

[0086] The polymer of the polymer particles may be polyacrylic acid (i.e., acrylic acid, acrylate, or polyacrylate), polyether, polyolefin, polyester, polyurethane, polycarbonate, polystyrene, or combinations thereof (i.e., copolymers or mixtures thereof, such as polyether-acrylate copolymers). The polymer may be an engineering plastic. Engineering plastics are a group of thermoplastic materials that have better mechanical and / or thermal properties than more widely used commercial plastics (such as polystyrene, polypropylene, and polyethylene). Examples of engineering plastics include acrylonitrile butadiene styrene (ABS), polycarbonate, and polyamide. Preferably, the polymer of the polymer particles is polyacrylic acid, polyether, polyolefin, polyester, or combinations thereof.

[0087] Individual particles may be made of one polymer or two or more polymers. Individual particles may be completely homogeneous or have a "core-shell" configuration with one, two, three or more "shell" layers, or have a gradient architecture (e.g., a continuously varying architecture). Such "core-shell" particles may include multi-stage latexes produced, for example, via emulsion polymerization of two or more different stages, emulsion polymerization using polymeric surfactants, or combinations thereof. Particle populations may include mixtures of polymers, including mixtures of homogeneous and core-shell particles.

[0088] The polymer particles may include polyester polymers. Suitable polyesters include polyesters formed from one or more suitable polycarboxylic acid components (e.g., dicarboxylic acid components, tricarboxylic acid components, tetracarboxylic acid components, etc.) and one or more suitable polyol components (e.g., diol components, triol components, polyol components having four hydroxyl groups, etc.). If desired, one or more other comonomers may be selectively used. Dicarboxylic acid components and diol components are preferred.

[0089] Suitable dicarboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (e.g., 2,6-naphthalenedicarboxylic acid) and furanic acid (e.g., 2,5-furanic acid); aliphatic dicarboxylic acids such as adipic acid, cyclohexanedicarboxylic acid, sebacic acid, and azelaic acid; unsaturated acids such as maleic anhydride, isocrine acid, and fumaric acid; and mixtures thereof. Other suitable polycarboxylic acids (or anhydrides) include phenylpentacarboxylic acid; phenylhexacarboxylic acid; 1,3,5,7-naphthyl-tetracarboxylic acid; 2,4,6-pyridine-tricarboxylic acid; pyrocalcite; trimellitic acid; pyromellitic acid; 3,5,3',5'-biphenyltetracarboxylic acid; 3,5,3',5'-bipyridyltetracarboxylic acid; 3,5,3',5'-benzophenonetetracarboxylic acid; 1,3,6,8-acridinitetetracarboxylic acid; 1,2,4,5-phenyltetracarboxylic acid; nadic anhydride; trimellitic anhydride; pyrocalcite anhydride, and mixtures thereof. Anhydrides or esters of the aforementioned acids, and mixtures of such acids, anhydrides, or esters may also be used.

[0090] Suitable diol components include, for example, polymethyl methacrylate (PMMA) represented by the formula HO-(CH2)n-OH (where n is about 2 to 10), such as ethylene glycol, propylene glycol, butanediol, hexanediol, and decanediol; branched diols represented by the formula HO-CH2-C(R2)-CH2-OH (where R is an alkyl group having 1 to 4 carbon atoms), such as neopentyl glycol; diethylene glycol and triethylene glycol; diols having a cyclohexane ring, such as cyclohexanediethanol (CHDM); 2-methyl-1,3-propanediol; diols having a cyclobutane ring, such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol; isosorbide; tricyclodecanediethanol; spirobicyclodiols (e.g., 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (PSG)); and mixtures thereof. Glycerin, trimethylolpropane (TMP) and other suitable trifunctional or higher polyols may be used alone or in combination with any other suitable polyol.

[0091] The polyester polymer particles are preferably made of semi-crystalline or crystalline polymers. Suitable exemplary crystalline and semi-crystalline polymers include polyethylene terephthalate (“PET”), copolymers of PET such as PET / I, polybutylene terephthalate (“PBT”), polyethylene naphthalate (“PEN”), poly(1,4-cyclohexanedimethyl terephthalate), and copolymers thereof and combinations thereof. Polyester materials may be formed from components including dimer fatty acids. Non-limiting examples of commercially available polyester materials may include polyesters commercially available under the trade name DYNAPOL, such as DYNAPOL L912 (including polycyclic groups derived from tricyclodecanediethanol), DYNAPOL L952, DYNAPOL P1500, DYNAPOL P1500 HV (having a melting point temperature of about 170°C, a glass transition temperature of about 20°C, and a number average molecular weight of about 20,000), DYNAPOL P1510, and DYNAPOL P1550 (available from Hiils AG, respectively, and based on monomers including terephthalic acid and / or isophthalic acid); polyester materials commercially available under the trade name TRITAN (available from Eastman Chemical Company, and based on monomers including 2,2,4,4-tetramethyl-1,3-cyclobutanediol); and polyester materials commercially available under the trade name GRILTEX, such as GRILTEX DD2267EG and GRILTEX. D2310EG (available from EMS-Chemie and based on monomers including terephthalic acid and / or isophthalic acid).

[0092] Exemplary polyester polymer systems that can be used to manufacture suitable polymer particles are described, for example, in U.S. Patent Publication No. 2014 / 0319133 (Castelberg et al.), U.S. Patent Publication No. 2015 / 0344732 (Witt-Sanson et al.), U.S. Patent Publication No. 2016 / 0160075 (Seneker et al.), International Application No. PCT / US2018 / 051726 (Matthieu et al.), U.S. Patent No. 5,464,884 (Nielle et al.), U.S. Patent No. 6,893,678 (Hirose et al.), and U.S. 7,198,849 (Stapfergenne et al.), U.S. Patent No. 7,803,415 (Kiefer-Liptak et al.), U.S. Patent No. 7,981,515 (Ambrose et al.), U.S. Patent No. 8,133,557 (Parekh et al.), U.S. Patent No. 8,367,171 (Stenson et al.), US In U.S. Patent No. 8,574,672 (Doreau et al.), U.S. Patent No. 9,096,772 (Lespinasse et al.), U.S. Patent No. 9,011,999 (Cavallin et al.), U.S. Patent No. 9,115,241 (Gao et al.), U.S. Patent No. 9,187,213 (Prouvost et al.), U.S. Patent No. 9,321,935 (Seneker et al.), U.S. Patent No. 9,650,176 (Cavallin et al.), U.S. Patent No. 9,695,264 (Lock et al.), U.S. Patent No. 9,708,504 (Singer et al.), U.S. Patent No. 9,920,217 (Skillman et al.), U.S. Patent No. 10,131,796 (Martinoni et al.), and U.S. Patent Publication No. 2020 / 0207516 (Seneker et al.).

[0093] Polyester polymers having a C4 ring may be used, such as those present in certain structural segments of compounds derived from cyclobutanediol type compounds, such as including 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Exemplary polyesters including such C4 rings are described, for example, in WO2014 / 078618 (KNOCTS et al.), U.S. Patent No. 8,163,850 (Marsh et al.), U.S. Patent No. 9,650,539 (Kuo et al.), U.S. Patent No. 9,598,602 (Kuo et al.), U.S. Patent No. 9,487,619 (Kuo et al.), U.S. Patent No. 9,828,522 (Argyropoulos et al.), and U.S. Patent Publication No. 2020 / 0207516 (Seneker et al.).

[0094] The polymers that can be used may also include polyvinylidene fluoride (PVDF) polymers. In many embodiments, the PVDF polymer contains at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, and most preferably is a homopolymer of repeating vinylidene fluoride units of the formula -[CH2CF2]-. Generally, PVDF materials with a higher vinylidene fluoride content are advantageous. PVDF polymers with this high vinylidene fluoride content can provide advantages over PVDF polymers with a lower vinylidene fluoride content because polymers with a higher vinylidene fluoride content may be more economical and more weather-resistant than compositions based on vinyl fluoride vinyl ethers (FEVE).

[0095] Optionally, in other embodiments where the PVDF polymer is not a homopolymer of vinylidene fluoride units, the PVDF polymer may include a polymer of one or more additional comonomers. Monomers that can be copolymerized with vinylidene fluoride typically include carbon-carbon double bonds, which may be allyl, styrene, vinyl, α-methylstyrene, (meth)acrylamide, cyanate, vinyl ether, (meth)acrylic acid moiety, or the like. Examples of such monomers may include ethylene, propylene, isobutylene, styrene, vinyl chloride, vinylidene chloride, dichlorofluoroethylene, trichlorofluoroethylene, tetrafluoroethylene, trifluoropropylene, hexafluoropropylene, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, N-butoxymethyl (meth)acrylamide, and isopropyl acetate. Others include monomers listed below for forming vinyl polymers. If thermosetting properties are required, such monomers may include crosslinking functional groups, such as -OH, -NCO, -COOH, -NH2, and combinations thereof. PVDF polymers may be thermoplastic or thermosetting, but thermoplastic embodiments are preferred.

[0096] The molecular weight (MW) of the PVDF polymer is preferably in the range of about 20,000 to about 500,000, more preferably about 20,000 to 400,000, even more preferably 20,000 to 300,000, and most preferably 50,000 to 200,000.

[0097] The polymers available in this disclosure may also include at least one thermoplastic polymer and / or at least one thermosetting polymer, wherein the vinylidene fluoride or other fluorine content of each such polymer is less than about 50% by weight, preferably less than about 20% by weight, more preferably less than about 10% by weight, and even 0% by weight. Thermoplastic and / or thermosetting polymers can provide many benefits. They can help improve the adhesion of the resulting coating to the substrate. The use of thermoplastic and thermosetting polymers may also tend to help improve the hardness and / or durability of the resulting coating. They can also help reduce costs, as using only fluorocarbon polymers may be too expensive and not cost-effective.

[0098] In addition, besides fluorocarbon polymers, the use of a combination of thermoplastic and thermosetting polymers can provide performance advantages, especially in preferred embodiments where both are present but the thermosetting content is limited. It has been found that when the coating is baked at relatively high temperatures and / or for relatively long times, clarity and gloss performance can be compromised when only thermoplastic or thermosetting polymers are present, rather than both. For example, if only thermoplastic polymers are present under such conditions, whitening may occur during boiling water testing, while if only thermosetting polymers are present, whitening may occur during baking. Furthermore, if too much thermosetting polymer is present, whitening may still occur during baking, even when used in combination with thermoplastic polymers. Therefore, it is generally desirable for the weight ratio of thermoplastic polymers to thermosetting polymers to be greater than about 2:1, and preferably in the range of about 2:1 to about 50:1, and more preferably about 2:1 to about 10:1. In a particular preferred embodiment, a weight ratio of about 4:1 is suitable. By limiting the thermosetting content in this way, the corresponding thermosetting content of the resulting coating will be reduced, and the tendency for whitening can be greatly avoided.

[0099] Each of the thermoplastic polymers and thermosetting polymers can independently have a wide range of molecular weights. As a general guideline, each can independently have a molecular weight (MW) in the range of about 5,000 to about 200,000, more preferably about 10,000 to about 150,000. In one embodiment, a suitable thermoplastic vinyl polymer derived from methyl methacrylate, ethyl acrylate, n-butyl methacrylate, and methacrylic acid has a molecular weight of 55,000. In one embodiment, a thermosetting vinyl polymer derived from methyl methacrylate, ethyl acrylate, and 2-hydroxyacrylate has a molecular weight of 16,200. When both thermoplastic and thermosetting polymers are used, the ratio of the molecular weight of the thermoplastic polymer to the molecular weight of the thermosetting polymer can vary in a wide range, but is generally in the range of about 1:4 to about 4:1, more preferably about 1:2 to about 2:1.

[0100] Various polymer materials can be used independently as thermosetting polymers and / or thermoplastic polymers. Examples of suitable materials include polyesters, polyurethanes, vinyl polymers such as poly(meth)acrylate polymers, polycarbonates, polyamides, polyureas, polyimides, polyurethanes, polycaprolactones, polysiloxanes, and combinations thereof. For outdoor use, polyurethanes and vinyl polymers are more suitable where weather resistance is desired, as they tend to be more weather-resistant than some other resins. Furthermore, it is desirable to limit or avoid aromatic components in outdoor applications, as these may be more prone to yellowing or degradation over time.

[0101] In many applications, the use of vinyl polymer materials for both thermoplastic and thermosetting polymers may be desirable, as industry has extensive experience and trust in combining such materials with PVDF polymers. As used herein, the term "vinyl polymer" refers to a polymer obtained by addition polymerization of one or more different kinds of monomers, oligomers, and / or polymers via carbon-carbon double bonds. Examples of carbon-carbon double bonds include allyl, styrene, vinyl or other olefinic, α-methylstyrene, (meth)acrylic acid, cyanate, vinyl ether, (meth)acrylic acid moiety, and / or the like. As used herein, the term "(meth)acrylic" encompasses acrylate and / or methacrylic acid. Various monomeric materials, oligomeric materials, and / or polymeric materials having one or more carbon-carbon double bonds can be used to form vinyl thermosetting or thermoplastic resins suitable for practicing the present invention. Such monomers, oligomers and / or polymers are advantageous for forming copolymers because many different types are commercially available and can be selected to have a variety of desired properties that help provide one or more desired performance characteristics.

[0102] Representative examples of monofunctional, polymerizable monomers suitable for forming vinyl polymers include styrene, α-methylstyrene, substituted styrene, vinyl esters, vinyl ethers, N-vinyl-2-pyrrolidone, (meth)acrylamide, vinylnaphthalene, alkylated vinylnaphthalene, alkoxyvinylnaphthalene, N-substituted (meth)acrylamide, octyl (meth)acrylate, nonylphenol ethoxylate (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile, β-cyanoethyl (meth)acrylate, 2-cyanoethoxyethyl (meth)acrylate, p-cyanostyrene, p-(cyanomethyl)styrene, isononyl (meth)acrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, isobutyl (meth)acrylate Alicyclic epoxides, α-epoxides, (meth)acrylonitrile, maleic anhydride, isoctyl methacrylate, lauryl (dodecyl) (meth)acrylate, stearyl (octadecyl) (meth)acrylate, beryllium methacrylate, n-butyl methacrylate, methyl methacrylate, trimethylcyclohexyl (meth)acrylate, ethyl methacrylate, hexyl methacrylate, methacrylic acid, N-vinylcaprolactone, stearyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, glycidyl methacrylate, vinyl acetate, and combinations thereof.

[0103] To provide copolymers with side-hydroxyl groups for crosslinking purposes, one or more hydroxyl-functional monomers, oligomers, and / or polymers may be incorporated into the final polymer. The side-hydroxyl groups of the copolymer not only promote the crosslinking, dispersion, and interaction of pigments in the formulation, but also promote the dispersion and interaction with other components in the composition. The hydroxyl groups may be primary, secondary, or tertiary hydroxyl groups, but are preferably primary and secondary hydroxyl groups. When used, the hydroxyl-functional monomer constitutes about 0.5 to 30% by weight, more preferably 1 to 25% by weight, of the monomer used to formulate the vinyl polymer.

[0104] Representative examples of suitable hydroxyl-functionalized monomers include various esters of α,β-unsaturated carboxylic acids having one or more diols, such as 2-hydroxyethyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyisobutyl (meth)acrylate, or 2-hydroxypropyl (meth)acrylate; 1,3-dihydroxypropyl-2-(meth)acrylate; 2,3-dihydroxypropyl-1-(meth)acrylate; adducts of α,β-unsaturated carboxylic acids with caprolactone; alkyl alcohol vinyl ethers, such as 2-hydroxyethyl vinyl ether; 4-vinylbenzyl alcohol; allyl alcohol; p-hydroxymethylstyrene; or similar.

[0105] Multifunctional materials, each molecule comprising more than one carbon-carbon double bond, can also be used to enhance various properties, such as crosslink density, hardness, scratch resistance, or similar properties. Examples of such higher functional monomers include ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, neopentyl tertrol tri(meth)acrylate, neopentyl tertrol tetra(meth)acrylate, and neopentyl glycol di(meth)acrylate, divinylbenzene, and combinations thereof.

[0106] The free radical reactive oligomeric materials and / or polymeric materials applicable to the present invention include, but are not limited to, (meth)acrylate esterified carbamate (i.e., carbamate (meth)acrylate), (meth)acrylate esterified epoxy resin (i.e., epoxy (meth)acrylate), (meth)acrylate esterified polyester (i.e., polyester (meth)acrylate), (meth)acrylate esterified (meth)acrylate, (meth)acrylate esterified polysiloxane, (meth)acrylate esterified polyether (i.e., polyether (meth)acrylate), (meth)acrylate vinyl ester, and (meth)acrylate esterified oil.

[0107] The vinyl polymer of the present invention can be prepared by a variety of additional polymerization techniques. In a preferred embodiment, the vinyl polymer of the present invention is prepared using free radical polymerization methods known in the art, including but not limited to bulk, solution, and dispersion polymerization methods. The resulting vinyl polymer can have various structures, including linear, branched, three-dimensional network, grafted structured, and combinations thereof.

[0108] The weight ratio of the PVDF polymer to the total weight of the thermoplastic and thermosetting polymers (if present) varies widely depending on a variety of factors, including but not limited to the desired end use of the resulting coating or the coated substrate. In a typical practice, the weight ratio of the PVDF polymer to the total weight of the thermoplastic and thermosetting polymers can range from about 0.3:1 to about 30:1.

[0109] It would be desirable to use a larger amount of PVDF polymer in this range. However, when both durability and elasticity are required in the end use, using too much PVDF polymer at the higher end of this range may not be desirable, such as when the coating of the present invention is formed on an exterior building panel. In a particular building panel application, the weight ratio of PVDF polymer to the total weight of thermoplastic and thermosetting polymers is 70:25, with an additional five parts by weight of amine plastic crosslinking agent used for every 70 parts by weight of PVDF polymer.

[0110] In some embodiments, the polymer particles may include a polyether polymer. The polyether polymer may contain a plurality of aromatic segments, more generally aromatic ether segments. The polyether polymer may be formed using any suitable reactants and any suitable polymerization process. The polyether polymer may be formed, for example, from reactants including: synergist compounds (e.g., diols, preferably polyphenols, more preferably diphenols; diacids; or compounds having both phenolic hydroxyl and carboxyl groups), and polyepoxides. In a preferred embodiment, the polyepoxide is a polyepoxide of a polyphenol (more generally, a diepoxide of a diphenol, such as propylene dioxide ether of a diphenol). Preferably, (i) the polyphenol compound is an ortho-substituted diphenol (e.g., tetramethylbisphenol F), (ii) the diepoxide is an ortho-substituted diphenol diepoxide (e.g., tetramethylbisphenol F), or (iii) both (i) and (ii).

[0111] Polyether polymers may be formed from reactants including diepoxides of ortho-substituted diphenols (e.g., tetramethylbisphenol F propylene dioxide ether) and diphenols having only one phenolic ring (e.g., hydroquinone, resorcinol, catechol, or their substituted variations).

[0112] Polyether polymers can be prepared from reactants comprising a diepoxide (generally propylene dioxide ether or diglycidyl ester), which is not derived from a polyphenol and comprises one or more main chains or side-attached aryl or heteroaryl groups. Such aromatic dioxides can be prepared, for example, from aromatic compounds (such as diols, diacids, diamines, etc.) having two or more reactive groups. Examples of such aromatic compounds suitable for forming aromatic dioxides include 1-phenyl-1,2-propanediol; 2-phenyl-1,2-propanediol; 1-phenyl-1,3-propanediol; 2-phenyl-1,3-propanediol; 1-phenyl-1,2-ethylenediol; vanillin; 1,2-, 1,3- or 1,4-benzenedimethanol; furanedimethanol (e.g., 2,5-furanedimethanol); terephthalic acid; isophthalic acid, etc.

[0113] Polyether polymers can be prepared from reactants comprising one or more aliphatic polyepoxides, which are generally aliphatic dioxides and more generally cycloaliphatic dieoxides. Exemplary aliphatic dieoxides include dieoxides of the following substances (generally propylene dioxide ethers): cyclobutanediol (e.g., 2,2,4,4-tetramethyl-1,3-cyclobutanediol), isosorbide, cyclohexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, tricyclodecanediol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (PSG), and mixtures thereof.

[0114] Exemplary reactants, polymerization processes, and polyether polymer systems that can be used to manufacture suitable polymer particles are described in U.S. Patent Nos. 7,910,170 (Evans et al.), 9,409,219 (Niederst et al.), 2013 / 0280455 (Evans et al.), 2013 / 0316109 (Niederst et al.), 2013 / 0206756 (Niederst et al.), 2015 / 0021323 (Niederst et al.), International Publications Nos. WO 2015 / 160788 (Valspar Sourcing), WO 2015 / 164703 (Valspar Sourcing), WO 2015 / 057932 (Valspar Sourcing), and WO In WO 2015 / 179064 (Valspar Sourcing) and WO 2018 / 125895 (Valspar Sourcing).

[0115] The polyether polymer may alternatively be formed from components that do not contain any bisphenol or any oxide of bisphenol, but unintentional trace amounts may be present due to, for example, environmental pollution. Examples of suitable reactants for forming such bisphenol-free polyether polymers include diepoxides derived from materials other than the bisphenols described in the patent documents mentioned in the preceding paragraphs, and any synergist compounds other than the bisphenols disclosed in such patent documents. Hydroquinone, catechol, resorcinol, and their substituted forms are non-limiting examples of suitable synergist compounds for preparing such bisphenol-free polyether polymers.

[0116] Preferably, the polymer particles may comprise polymers formed via free radical polymerization of olefinic unsaturated monomers, wherein acrylic polymers are preferred examples of such polymers. For convenience, such polymers are referred to herein as "acrylic polymers," and it is assumed that such polymers generally comprise one or more monomers selected from (meth)acrylates or (meth)acrylic acid. Preferred acrylic polymers include acrylic polymers polymerized by organic solution polymerization and acrylic latex polymers polymerized by emulsion polymerization. Suitable acrylic polymers comprise reaction products of components including (meth)acrylates, optional ethylene unsaturated monofunctional or multifunctional acids, and optional vinyl compounds. For example, acrylate film-forming polymers may be reaction products of components including ethyl acrylate, acrylic acid and styrene (preferably in the presence of 2,2'-azabis(2-methyl-butyronitrile), and tributyl peroxybenzoate without a free radical initiator.

[0117] Examples of suitable (meth)acrylates (i.e., methacrylates and acrylates) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, octyl (meth)acrylate, and nonyl (meth)acrylate. Any suitable isomer or combination of isomers of the above may be used. For example, the disclosure of "(meth)acrylate" is intended to disclose all isomers, such as n-butyl (meth)acrylate, dibutyl (meth)acrylate, terbutyl (meth)acrylate, etc. Generally, as disclosed herein, unless specifically indicated to the contrary, it is intended to disclose all isomers for a given monomer.

[0118] Examples of suitable alkenyl unsaturated monofunctional or polyfunctional acids include methacrylic acid, acrylic acid, crotonic acid, itaconic acid, maleic acid, medoconic acid, citric acid, sorbic acid, and fumaric acid.

[0119] Examples of suitable vinyl compounds include styrene, halostyrene, isoprene, conjugated butadiene, α-methylstyrene, vinyltoluene, vinylnaphthalene, vinyl chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinylcyclohexane, vinylcyclooctane, vinylcyclohexene, and vinyl stearate.

[0120] Examples of commercially available acrylic polymers include those available under the trade names VIACRYL SC 454 / 50BSNB, VIACRYL SC383w / 50WA and VANCRYL 2900 DEV (all from Cytec Industries Inc., West Patterson, NJ), and NEOCRYL A-639, NEOCRYL XK-64, URACON CR203 M3 and URACON CS113 S1G (all from DSM Neoresins BV, 5140 AC Waalwijk, Netherlands).

[0121] Exemplary acrylic polymer systems that can be used to manufacture suitable polymer particles are described in U.S. Patent No. 8,168,276 (Cleaver et al.), U.S. Patent No. 7,189,787 (O'Brien), U.S. Patent No. 7,592,047 (O'Brien et al.), U.S. Patent No. 9,181,448 (Li et al.), U.S. Patent No. 9,394,456 (Rademacher et al.), U.S. Patent Publication No. 2016 / 0009941 (Rademacher et al.), U.S. Patent Publication No. US2016 / 0376446 (Gibanel et al.), and U.S. Patent Publication No. 2017 / 0002227 (Gibanel et al.). In Publication Nos. 2018 / 0265729 (Gibanel et al.), WO2016 / 196174 (Singer et al.), WO2016 / 196190 (Singer et al.), WO2017 / 112837 (Gibanel et al.), WO2017 / 180895 (O'Brien et al.), WO2018 / 085052 (Gibanel et al.), WO2018 / 075762 (Gibanel et al.), WO2019 / 078925 (Gibanel et al.), WO2019 / 046700 (O'Brien et al.), and WO2019 / 046750 (O'Brien et al.).

[0122] The polymer particles may include dried latex particles, which include both polyether polymers and acrylic polymers. Examples of such latex particles are described, for example, in WO2017 / 180895 (O'Brien et al.) and International Application No. WO2019046700 (O'Brien et al.).

[0123] Preferably, the polymer particles may include polyolefin polymers. Examples of suitable polyolefin polymers include maleic acid modified polyethylene, maleic acid modified polypropylene, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, propylene-acrylic acid copolymer, propylene-methacrylic acid copolymer, and ethylene-vinyl alcohol copolymer.

[0124] Examples of commercially available polyolefin polymers include those acquired under the trade names DOW PRIMACOR 5980i, DUPONT NUCREL, POLYBOND 1103, NIPPON SOARNOL (EVOH), ARKEMA OREVAC 18751, and ARKEMA OREVAC 18360. Exemplary polyolefin polymers that can be used to manufacture suitable polymer particles are described in U.S. Patent No. 9,000,074 (O'Brien), U.S. Patent No. 8,791,204 (O'Brien), International Publication No. WO 2014 / 140057 (Akzo Nobel), U.S. Patent No. 8,722,787 (Romick et al.), U.S. Patent No. 8,779,053 (Lundgard et al.), and U.S. Patent No. 8,946,329 (Wilbur et al.).

[0125] Suitable polyolefin particles can be prepared from aqueous dispersions of polyolefin polymers. See, for example, U.S. Patent No. 8,193,275 (Moncla et al.) for a description of a process suitable for producing such aqueous polyolefin dispersions. Examples of commercially available aqueous polyolefin dispersions include CANVERA products available from Dow, including, for example, CANVERA 1110, CANVERA 3110 series, and CANVERA 3140 series.

[0126] The polymer particles may include an unsaturated polymer, which is combined with one or both of an ether component or a metal desiccant. The ether component may be present in the unsaturated polymer itself. While not wishing to be bound by theory, it is believed that the combination of a suitable amount of unsaturated material (e.g., aliphatic or cycloaliphatic carbon-carbon double bonds, such as those present in maleic anhydride, isocrine, functionalized polybutadiene, and similar derivatives of norbornene groups and saturated structural units) with a suitable amount of ether component or metal desiccant (e.g., aluminum, cobalt, copper, their oxides, their salts) can result in molecular weight accumulation during the thermosetting of the liquid-jet or aerosol-jet composition to form a cured coating. See, for example, U.S. Patent No. 9,206,332 (Cavallin et al.) for further discussion of such reaction mechanisms and suitable materials and concentrations. The polymer of the polymer particles may have an iodine value of at least 10, at least 20, at least 35, or at least 50. There is no particular upper limit to the appropriate iodine value, but in most such embodiments, the iodine value generally does not exceed about 100 or about 120. The aforementioned iodine value is expressed in centigs of iodine per gram of material. The iodine value can be determined, for example, using ASTM D 5768-02 (re-approved in 2006), entitled "Standard Test Method for Determining the Iodine Value of High-Oil Fatty Acids." Optional Additives

[0127] The liquid jet or aerosol inkjet coating composition disclosed herein may include one or more other optional additives to provide the desired effect. For example, such optional additives may be included in the coating composition to enhance the aesthetics of the composition, thereby facilitating the manufacture, handling, transport and application of the composition, and further improving the specific functional properties of the coating composition or a hardened coating produced therefrom. One or more optional additives may form part of the particles themselves.

[0128] Examples of such optional additives include, for example, lubricants, adhesion promoters, crosslinking agents, catalysts, colorants (e.g., pigments or dyes), ferromagnetic particles, degassing agents, leveling agents, wetting agents, surfactants, flow control agents, heat stabilizers, corrosion inhibitors, tackifiers, inorganic fillers, metal desiccants, and combinations thereof. Liquid-jet or aerosol-jet coating compositions may include one or more lubricants, pigments, crosslinking agents, or combinations thereof.

[0129] In a preferred embodiment, the liquid jet or aerosol inkjet coating composition disclosed herein includes one or more lubricants, for example, for flexibility. In this context, the lubricant is a compound that reduces friction at the coating surface to impart abrasion resistance to the final coated metal substrate. This differs from flow modifiers, which facilitate the flow of the coating composition and the application of the coating to a metal substrate.

[0130] Examples of suitable lubricants include cannabal wax, synthetic waxes (e.g., Fischer-Tropsch wax), polytetrafluoroethylene (PTFE) wax, polyolefin waxes (e.g., polyethylene (PE) wax, polypropylene (PP) wax, and high-density polyethylene (HDPE) wax), amide waxes (e.g., micronized ethylene-bis-stearamide (EBS) wax), combinations thereof, and modified forms thereof (e.g., amide-modified PE wax, PTFE-modified PE wax, and the like). The lubricant may be a micronized wax, optionally in spherical form. The lubricant imparts flexibility to the coated metal substrate by providing lubrication, which is beneficial for metal cans, particularly for the manufacture of riveted can ends and pull tabs.

[0131] Based on the total solids content of the coating composition (i.e., the total weight of the cured layer), one or more lubricants may be present in the liquid-jet or aerosol-jet coating composition disclosed herein in an amount of at least 0.1 wt%, at least 0.5 wt%, or at least 1 wt%. Furthermore, based on the total solids content of the coating composition (i.e., the total weight of the cured layer), one or more lubricants may be present in an amount of at most 4 wt%, at most 3 wt%, or at most 2 wt%. The concentration in the cured coating is equal to the concentration of the starting material in the liquid-jet or aerosol-jet coating composition.

[0132] The lubricant may be present in the polymer particles, on the polymer particles, in another component used to form a liquid-jet or aerosol-jet coating composition, or in a combination thereof. The lubricant may also be applied in a second liquid-jet or aerosol-jet coating composition applied in a separate layer.

[0133] Examples of suitable commercially available lubricants include CERETAN series products from Munzig (e.g., CERETAN MA 7020, MF 5010, MM 8015, MXF 2999, MT 9120, MXD 3920, and MXF 9899); LUBA-PRINT series products from Munzig (e.g., LUBA-PRINT 255 / B, 276 / A (ND), 351 / G, 501 / S-100, 749 / PM, and CA30); SST-52, S-483, FLUOROSLIP 893-A, TEXTURE 5347W, and SPP-10 products from Shamrock; and BYK series products from CERAFLOUR (e.g., CERAFLOUR). Products 981, 988, 996, 258, 970 and 916); and CERACOL 607 products from BYK.

[0134] The particle size of some of these lubricants and the methods for determining such particle size as identified by the supplier (however, in this document, such lubricant particle size can be measured by laser diffraction particle size analysis) are presented in the table below. supplier lubricant Chemistry of Lubricants* granularity* method* Munzing Ceretan MA 7020 Micronized ethylene-bis-stearamide wax D99 < 20 µm / D50 < 5 µm LV 5 ISO 13320 Munzing Ceretan MF 5010 Spherical, micronized PTFE-modified polyolefin wax D99 < 10 µm / D50 < 4 µm LV 5 ISO 13320 Munzing Ceretan MM 8015 Spherical, micronized lignite wax D99 < 15 µm / D50 < 6 µm LV 5 ISO 13320 Munzing Ceretan MXF 2999 Micronized functional blends coated with PTFE D50 < 50 µm LV 5 ISO 13320 Munzing Ceretan MT 9120 High-melting-point, spherical, micronized Fischer-Tropsch wax D99 < 20 µm / D50 < 7 µm LV 5 ISO 13320 Munzing Ceretan MXD 3920 A coated, micronized wax with diamond-like hardness D99 < 20 µm / D50 < 4 µm LV 5 ISO 13320 Munzing Ceretan MXF 9899 Spherical, micronized functionalized blends with PTFE coating D50 < 50 µm LV 5 ISO 13320 Munzing LUBA-print 255 / B Kanaba wax dispersion D50: 2-3 µm / D98: < 6 µm Picture-Particle-Analyzing System Munzing LUBA-print 276 / A Polyethylene wax / PTFE dispersion D50: 2-3 µm / D98: < 8 µm Photo Particle Analysis System Munzing LUBA-print 351 / G Functional blended wax dispersion D50: 2-3 µm / D98: < 5 µm Photo Particle Analysis System Munzing LUBA-print 501 / S-100 Polyethylene wax dispersion D50: 2.5-4 µm / D98: < 8 µm Photo Particle Analysis System Munzing LUBA-print 749 / PM amide-wax dispersion D50: 2-3 µm / D98: < 5 µm Photo Particle Analysis System Munzing LUBA-print CA 30 Kanaba wax dispersion D98: 3.0 µm Single-pass test BYK Ceraflour 981 Micronized PTFE D50: 3 µm / D90: 6 µm Laser diffraction - volume distribution BYK Ceraflour 988 Micronized and amide-modified polyethylene wax D50: 6 µm / D90: 13 µm Laser diffraction - volume distribution BYK Ceraflour 996 Micronized, PTFE-modified polyethylene wax D50: 6 µm / D90: 11 µm Laser diffraction - volume distribution BYK Ceraflour 970 Micronized polypropylene wax D50: 9 µm / D90: 14 µm Laser diffraction - volume distribution BYK Ceraflour 916 Micronized and modified HDPE wax / polymer mixture D50: 46 µm / D90: 82 µm Laser diffraction - volume distribution BYK Ceramat 258 Dispersion of oxidized HDPE wax 30 µm Hegman BYK Ceracol 607 PTFE-modified polyethylene wax dispersion D50: 4 µm / D90: 10 µm Laser diffraction - volume distribution *Based on the manufacturer's documentation

[0135] In a preferred embodiment, the liquid jet or aerosol inkjet coating composition disclosed herein includes one or more crosslinking agents and / or catalysts. Additionally, or alternatively, the liquid jet or aerosol inkjet coating composition may include one or more self-crosslinkable polymers. Examples of suitable crosslinking agents (e.g., phenolic crosslinking agents, amino crosslinking agents, or combinations thereof) and catalysts (e.g., titanium-containing catalysts, zirconium-containing catalysts, or combinations thereof) are described in U.S. Patent No. 8,168,276 (Cleaver et al.).

[0136] The term "crosslinker" refers to a molecule capable of forming covalent bonds between polymers or between two different regions of the same polymer. Examples of suitable crosslinkers include carboxyl-reactive curing resins, with β-hydroxyalkyl-amide crosslinkers being preferred (e.g., commercially available under trade names from EMS-Griltech (e.g., PRIMID XL-552 and PRIMID QM-1260 products)), and hydroxyl-curing resins, such as, for example, phenolic crosslinkers, end-capped isocyanate crosslinkers, and amino plastic crosslinkers. Other suitable curing agents may include benzo[a]₂ curing agents, such as, for example, benzo[a]₂-based phenolic resins or hydroxyalkyl ureas. Examples of benzo[a]₂-based curing agents are provided in U.S. Patent Publication No. 2016 / 0297994 (Kuo et al.). Examples of hydroxyalkyl ureas are provided in U.S. Patent Publication No. 2017 / 0204289 (Kurtz et al.).

[0137] Phenolic crosslinking agents include condensation products of aldehydes and phenols. Formaldehyde and acetaldehyde are preferred aldehydes. Various phenols can be used, such as phenol, cresol, p-phenol, p-tert-phenol, p-tert-pentylphenol, and cyclopentylphenol.

[0138] The powdered polymer particles of the present invention may optionally include a crosslinking agent to promote crosslinking of the thermosetting polymer in the presence. In a preferred embodiment where the thermosetting polymer includes hydroxyl functional groups, an amino plastic crosslinking agent may be preferred. These products may have a wide range of molecular weights. Some may be monomers, oligomers, or polymers. Amino plastic crosslinking agents are generally condensation products of aldehydes (such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde) and substances containing amino or amide groups (such as urea, melamine, and benzoguanamine). Examples of suitable amino plastic crosslinking resins include benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, esterified melamine-formaldehyde, and urea-formaldehyde resins. A specific example of a suitable amino plastic crosslinking agent is a fully alkylated melamine-formaldehyde resin commercially available under the trade name CYMEL 303 from Cytec Industries, Inc.

[0139] Condensation products of other amines and amides can also be used as crosslinking agents for amine plastics, such as aldehyde condensates of triazoles, diazoles, triazoles, guanidines, guanidines, and alkyl-substituted melamines. Some examples of such compounds are N,N'-dimethylurea, benzourea, dicyandiamide, methylguanidine, acetoguanidine, diglucopyranourea, 2-chloro-4,6-diamino-1,3,5-tris, 6-methyl-2,4-diamino-1,3,5-tris, 3,5-diaminotriazoles, triaminopyrimidines, 2-mercapto-4,6-diaminopyrimidines, 3,4,6-tris(ethylamino)-1,3,5-tris, etc. Although formaldehyde is the most commonly used aldehyde, other similar condensation products can be made from other aldehydes, such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal, etc.

[0140] Preferred amino plastic crosslinking agents are simply condensates of formaldehyde and amines, preferably melamine, to provide thermosetting hydroxymethyl functional resins. Although many amino plastic resins are widely available, such as urea-formaldehyde condensates and benzoguanamine-formaldehyde condensates, preferred amino plastic resins are polyalkoxymethyl melamine resins in which the alkoxy group contains 1 to 4 carbon atoms. Suitable melamine-formaldehyde condensates are well known to be readily available commercially and are typically etherified with lower alcohols for use in organic solvent solutions. Examples of suitable amino plastic curing agents include etherified melamine-formaldehyde condensates (e.g., polymethoxymethyl melamine, available under the trade name CYMEL 303 from Cytec) as solutions in organic solvents. Amino plastic resins are typically present in an amount of 0.1 wt% to 10 wt% of total resin solids, and more preferably in an amount of 0.2 wt.% to 3.0 wt.% of total resin solids.

[0141] Although amine-based plastic resins are preferred for curing hydroxyl-functionalized copolymers, any curing agent that reacts with hydroxyl functional groups, such as phenolic resins or end-capped polyisocyanates, may also be used. Suitable end-capped isocyanate curing agents include isophorone diisocyanates end-capped with methyl ethyl ketone oxime or 2,4-toluene diisocyanates end-capped with octyl alcohol. The types of end-capped isocyanate curing agents are well known, and it is well known that these agents achieve curing by forming carbamate groups on the coating composition when baking causes the end-capped isocyanate groups to dissociate and become active.

[0142] Desiredly, a catalyst can be used according to conventional practice to promote the crosslinking reaction between the hydroxyl-functional thermosetting resin and the amine-based plastic crosslinking agent. According to a representative method, a capped acid catalyst is used in a suitable amount. The acid is capped with a suitable thermally unstable masking group such as an amine, making the coating composition substantially non-reactive at room temperature and exhibiting good storage stability. However, upon heating, the capped amine groups disengage, allowing the catalyst to become active and catalytically promote crosslinking.

[0143] In a preferred embodiment, the liquid jet or aerosol inkjet coating composition disclosed herein includes one or more colorants (such as pigments and / or dyes). Examples of suitable colorants for use in liquid jet or aerosol inkjet coating compositions include titanium dioxide, barium sulfate, carbon black, and iron oxide, and may also include organic dyes and pigments.

[0144] One or more colorants may be present in the liquid-jet or aerosol-jet coating composition disclosed herein, in an amount of, for example, at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt%, or at least 15 wt%, based on the total solids content of the coating composition (i.e., the total weight of the cured coating). They may be present in an amount of, at most 50 wt%, at most 40 wt%, at most 30 wt%, or at most about 20%, based on the total solids content of the coating composition (i.e., the total weight of the cured coating). The concentration in the cured coating is equal to the concentration of the starting material in the liquid-jet or aerosol-jet coating composition. Using a higher colorant concentration can help achieve good coverage with a thinner coating.

[0145] In some embodiments, the liquid-jet or aerosol-jet coating composition disclosed herein includes one or more pigments. Suitable pigments may include, for example, titanium dioxide, silicon dioxide, iron oxides of various colors, various silicates (e.g., talc, diatomaceous earth, asbestos, mica, clay, lead silicate, etc.), zinc oxide, zinc sulfide, zirconium oxide, graphite powder, carbon black, barium carbonate, barium sulfate, etc. Floating and non-floating metallic pigments may also be used. Organic pigments known to be stable at the temperatures used for curing or baking the first coating composition may also be used. Commercially available forms of coating compositions include, for example, Valspar's FLUROPON or VALFLON, which can be used across a wide color space. Therefore, in one embodiment, the first coating composition described herein preferably includes at least one pigment present in an amount of preferably about 1 wt% to 20 wt%, more preferably about 5 wt% to 15 wt%, based on the total weight of the first coating composition.

[0146] The liquid-jet or aerosol-jet coating composition disclosed herein may include one or more inorganic fillers. Exemplary inorganic fillers used in the liquid-jet or aerosol coating composition disclosed herein include, for example, clay, mica, aluminosilicate, fuming silica, magnesium oxide, zinc oxide, barium oxide, calcium sulfate, calcium oxide, aluminum oxide, magnesium aluminum oxide, zinc aluminum oxide, magnesium titanium oxide, iron titanium oxide, calcium titanium oxide, and mixtures thereof.

[0147] The inorganic filler is preferably non-reactive and can be incorporated into the liquid spray or aerosol spray coating composition in the form of particles, preferably with a particle size distribution equal to or less than the particle size distribution of one or more polymer particle blends.

[0148] Based on the total solids content of the coating composition (i.e., the total weight of the cured layer), one or more inorganic fillers may be present in the liquid-jet or aerosol-jet coating composition disclosed herein in an amount of at least 0.1 wt%, at least 1 wt%, or at least 2 wt%. Based on the total solids content of the coating composition (i.e., the total weight of the cured layer), one or more inorganic fillers may be present in an amount of at most 20 wt%, at most 15 wt%, or at most 10 wt%. The concentration in the cured coating is equal to the concentration of the starting material in the liquid-jet or aerosol-jet coating composition.

[0149] In a preferred embodiment, the liquid-jet or aerosol-jet coating composition disclosed herein includes one or more surfactants. Examples of suitable surfactants for use in liquid-jet or aerosol-jet coating compositions include wetting agents, emulsifiers, suspending agents, dispersants, and combinations thereof. One or more of the surfactants may be polymeric surfactants (e.g., alkali-soluble resins). Examples of suitable surfactants for use in coating compositions include nonionic and anionic surfactants.

[0150] One or more surfactants may be present in the liquid-jet or aerosol-jet coating composition disclosed herein in an amount of at least 0.1 wt% or at least 0.2 wt% based on the total solids content of the coating composition (i.e., the total weight of the cured layer as a whole). One or more surfactants may be present in an amount of up to 10 wt% or up to 5 wt% based on the total solids content of the coating composition (i.e., the total weight of the cured layer as a whole).

[0151] Standard mixing methods can be used to form a water-based dispersion. (After coating the substrate)

[0152] This disclosure also provides a coated substrate. The hardened (e.g., cured) coating of this disclosure is preferably adhered to metals (e.g., steel, stainless steel, tin-free steel (TFS), tin-plated steel, electrolytic tin plate (ETP), aluminum, etc.).

[0153] Substrates applicable herein may include metals, wood, paper, ceramics and glass, polymers, leather, woven and nonwoven fabrics, fibers, combinations thereof (regardless of whether synthetic or natural), etc. Particularly suitable substrates include steel, aluminum, zinc, copper and alloys, intermetallic compositions, composites including one or more of these, and / or the like. Non-limiting examples of metallic substrates that may benefit from having the coating composition of the present invention applied to their surface include hot-rolled steel, cold-rolled steel, hot-dip galvanized, electro-galvanized, aluminum, tinplate, various grades of stainless steel, and aluminum-zinc alloy coated sheet steel (e.g., GALVALUME sheet steel). Representative supplies of substrates include, but are not limited to, extrusions, coils, or other manufactured substrates intended to be converted into, for example, building panels, roof panels, automotive body parts, aluminum extrusions, and the like.

[0154] Available substrates may include those having variable thicknesses, which may depend at least in part on their characteristics, the end purpose of the coated substrate, desired characteristics, one or more final articles formed therefrom, or any combination thereof. In some embodiments, the available average thickness of the substrate may be not less than 0.005 inches, not less than 0.007 inches, not less than 0.008 inches, not less than 0.010 inches, not less than 0.012 inches, or even not less than 0.014 inches. In some embodiments, the available average thickness of the substrate may be not greater than 0.05 inches, not greater than 0.04 inches, not greater than 0.03 inches, not greater than 0.029 inches, or even not greater than 0.025 inches. In some preferred embodiments, for example, available substrates may include those with an average thickness of 0.010 inches to 0.025 inches, or even 0.014 inches to 0.025 inches.

[0155] Available substrates may include rolls of material having various sizes. For example, in some embodiments, available rolls may include roll widths of, for example, not less than 12 inches, not less than 24 inches, not less than 36 inches, or even not less than 40 inches (the width of the roll can be considered as a dimension perpendicular to the direction in which the roll is rolled up and / or unrolled). For example, in some embodiments, available rolls may include roll widths of, for example, not greater than 144 inches, not greater than 96 inches, not greater than 72 inches, or even not greater than 60 inches.

[0156] In the context of a hardened adhesive coating being applied to a surface and then to a substrate, this includes two coatings: one applied directly (e.g., pure metal or pretreated metal, such as electroplated steel) and the other applied indirectly (e.g., on a primer layer) to the surface or substrate. Thus, a coating applied, for example, to a pretreated layer (e.g., formed from a chromium- or chromium-free pretreated layer) or to a primer layer overlying the substrate constitutes a coating applied to (or disposed on) the substrate.

[0157] If steel sheet is used as the metal substrate, the surface treatment may include one, two or more surface treatments, such as zinc plating, tin plating, nickel plating, electrolytic chromate treatment, chromate treatment, and phosphate treatment. If aluminum sheet is used as the metal substrate, the surface treatment may include inorganic chemical conversion treatment, such as chromium phosphate treatment, zirconium phosphate treatment, or phosphate treatment; organic / inorganic composite chemical conversion treatment based on a combination of inorganic chemical conversion treatment and organic components, such as water-soluble resins (such as acrylic resins or phenolic resins) and tannic acid; and application-type treatment based on a combination of water-soluble resins (such as acrylic resins) and zirconium salts.

[0158] The metal substrate can be cryogenically cleaned. It can be provided as a cryogenically cleaned metal substrate, or the coating method can include cryogenically cleaning the metal substrate before guiding the powder coating composition to at least a portion of the substrate. In an exemplary process, cryogenic cleaning can be achieved by guiding a high-pressure liquid nitrogen stream (between 5000 psi and 50,000 psi and between 150℉ and 250℉) to the metal surface. The temperature of the metal surface drops rapidly, causing any contaminants to break down. The broken contaminants are then guided away from the metal surface by the high-pressure stream, leaving the cleaned substrate.

[0159] In some embodiments, the hardened adhesive coating is continuous. Therefore, it is free from pinholes and other coating defects that could lead to exposed substrate, potentially resulting in (i) unacceptable corrosion of the substrate, and even pores and product leakage in the substrate, and / or (ii) adulteration of the packaged product. Except in embodiments requiring a certain degree of roughness or texture (e.g., for some external can coatings for aesthetic purposes), the hardened continuous coating is preferably smooth, especially for most internal can coatings.

[0160] In some embodiments, the cured continuous adhesive coating has an average thickness of up to 100 micrometers (particularly when the coating has a texture), or a maximum thickness of up to 100 micrometers. Preferably, the cured continuous adhesive coating has an average thickness of up to 60 micrometers, up to 55 micrometers, up to 50 micrometers, up to 45 micrometers, or even up to 35 micrometers. Preferably, the cured continuous adhesive coating has an average thickness of, for example, not less than 1 micrometer, not less than 10 micrometers, not less than 24 micrometers, not less than 30 micrometers, or even not less than 45 micrometers. Without being limited by theory, a coating thickness of less than 1 micrometer will not include sufficient pigment to provide the desired color intensity to the cured film. On the other hand, a coating thickness greater than 40 micrometers will result in a brittle film that can be bent or cracked when a coated article is formed from the substrate. In some embodiments, more than one first coating layer may be applied, and in this case, the total thickness of the first coating layer may vary from preferably about 30 to 60 micrometers, more preferably 45 to 55 micrometers.

[0161] The liquid-jet or aerosol-jet coating compositions disclosed herein can also be used on several types of substrates and in a wide variety of applications, including, for example, metal building panels, metal roofs, sidings, garage doors, office furniture, household appliances, heating and cooling panels, automotive panels and components, and the like. The liquid-jet or aerosol-jet coating compositions can be applied to sheet metal by spraying, dipping, or brushing, such as for lighting fixtures, architectural metal surfaces (e.g., sink materials, curtains, sidings, and window frames), but are particularly suitable for roll-to-roll coating operations where the liquid-jet or aerosol-jet coating compositions are applied to the sheet as it is unwound from the roll and then baked as the sheet travels up the winding machine. It is further envisioned that the liquid-jet or aerosol-jet coating compositions of the present invention can be used for a variety of other end uses, including industrial coating applications, such as, for example, appliance coatings; encapsulation coating applications; internal or external steel building products; HVAC applications; agricultural metal products; wood coatings, etc.

[0162] In some embodiments, the substrate may be in the form of a planar roll or sheet. Sheet coating involves applying a coating composition to a separate substrate sheet that has been pre-cut into square or rectangular "sheets". Roll-to-roll coating is a particular application method in which a wound metal strip (e.g., aluminum) is unwound and then passed through pretreatment, coating, and drying equipment before being finally rewound. It is believed that the use of the preferred liquid-jet or aerosol-jet coating compositions disclosed herein can eliminate the pretreatment steps used when using conventional liquid coatings, thereby simplifying the application process and reducing removal costs. Roll-to-roll coating allows for highly efficient coating of large surface areas in a short time with high throughput. Therefore, the process of applying liquid-jet or aerosol-jet coating compositions to substrates according to the present disclosure is preferably used in roll-to-roll coating processes or sheet coating processes.

[0163] The hardened coating may be formed from a liquid-jet or aerosol-jet coating composition having or not having one or more optional additives, particularly having the polymer particles and lubricant described herein, as described herein. The lubricant may be present in the hardened coating within the polymer particles, on the polymer particles, in another component used to form the liquid-jet or aerosol-jet coating composition (or the hardened coating formed therefrom), or in a combination thereof. Alternatively or additionally, the lubricant described herein (e.g., cannabal wax, synthetic wax, polytetrafluoroethylene wax, polyethylene wax, polypropylene wax, or combinations thereof) may be incorporated into or onto the hardened coating, based on the total solids content of the liquid-jet or aerosol-jet coating composition (i.e., the total weight of the overall hardened coating). The lubricant is preferably present in an amount of at least 0.1 wt% (or at least 0.5 wt% or at least 1 wt%), and preferably in an amount of at most 4 wt% (or at most 3 wt% or at most 2 wt%). The concentration in the hardened coating is equal to the concentration of the starting material in the liquid-jet or aerosol-jet coating composition.

[0164] Preferably, the hardened coating comprising an amorphous polymer (and / or a semi-crystalline polymer having an amorphous portion) has a glass transition temperature (Tg) of at least 15°C, at least 20°C, or at least 25°C, and a Tg of at most 150°C, at most 125°C, at most 110°C, at most 100°C, at most 80°C, or at most 50°C. For many encapsulation technologies, especially for internal can coatings used for more corrosive products, higher Tg coatings are preferable for corrosion resistance.

[0165] The hardened coating may not have any detectable Tg.

[0166] Preferably, when the coating for an internal beverage can is applied to a conventional aluminum beverage can endstock at a known average dry film coating weight (e.g., approximately 2.3 g / m² for an internal soda can coating), the hardened coating produced by the preferred embodiment of the liquid-jet or aerosol-jet coating composition is able to pass the 4T T-bend test. The available T-bend test procedure is described in ASTM D4145-10 (re-approved in 2010, 2018).

[0167] The coated articles described herein exhibit the best weathering or weather resistance. "Weather resistance" refers to the coating's resistance to degradation when exposed to UV radiation (i.e., sunlight) for an extended period. Weathering can be determined using the weathering test described in the examples section, which measures the coated substrate's ability to exhibit the best weathering.

[0168] The coated substrate disclosed herein can be stretched and re-stretched. Importantly, the coating on the resulting thinned substrate remains continuous and adherent. Coating Method

[0169] This disclosure provides a method for forming a coated substrate or an article comprising a coated substrate, which relates to forming a patterned coating. This method uses various liquid-jet or aerosol-jet coating compositions comprising polymer particles and additives, and any of the general systems and methods described herein. The general description of the coating also applies to coatings obtained by this method.

[0170] For example, in some embodiments, the disclosed method may include: providing a liquid-jet or aerosol-jet coating composition as described herein; directing the liquid-jet or aerosol-jet coating composition to at least a portion of the substrate; and providing effective conditions for forming a hardened, continuously adhered coating on at least a portion of the substrate with the liquid-jet or aerosol-jet coating composition.

[0171] In another embodiment, a coating method includes: providing a substrate; providing a liquid-jet or aerosol-jet coating composition as described herein; selectively applying the liquid-jet or aerosol-jet coating composition to at least a portion of the substrate to form a patterned coating; and providing effective conditions for forming a hardened, adhesive patterned coating on at least a portion of the substrate using the liquid-jet or aerosol-jet coating composition. This is a method of selectively applying or printing a liquid-jet or aerosol-jet coating composition.

[0172] In another embodiment, a coating method includes applying multiple layers of the liquid-jet or aerosol-jet coating compositions disclosed herein. More than two (e.g., three or more, four or more, or five or more) different liquid-jet or aerosol-jet coating compositions may be applied to form a cured coating. These different liquid-jet or aerosol-jet coating compositions will generally differ in at least one physical or chemical property. Representative such properties may include, for example, polymer particle properties such as molecular weight, density, glass transition temperature (Tg), melt temperature (Tm), intrinsic viscosity (IV), melt viscosity (MV), melt index (MI), crystallinity, block or segment arrangement, availability of reactive sites, reactivity, acid value, and coating composition properties such as surface energy, hydrophobicity, oleophobicity, moisture or oxygen permeability, transparency, heat resistance, resistance to sunlight or ultraviolet energy, adhesion to metals, color or other visual effects, and recyclability. For properties measured on an absolute scale, for example, different properties (i.e., specific properties of at least two different liquid jet or aerosol jet compositions) may differ by at least ±5%, at least ±10%, at least ±15%, at least ±25%, at least ±50%, at least ±100%, or more.

[0173] Therefore, in one embodiment, this disclosure provides a method of coating a substrate, the process comprising: providing a substrate; providing a plurality of liquid-jet or aerosol-jet coating compositions, wherein at least two of the plurality of liquid-jet or aerosol-jet compositions are different; directing each of the plurality of coating compositions to at least a portion of the substrate such that at least one coating composition is deposited on another different coating composition (before or after the underlying coating composition has hardened to form a coating); and providing effective conditions for the plurality of liquid-jet or aerosol-jet coating compositions to form a hardened, continuously adherent coating on at least a portion of the substrate.

[0174] The multilayer structure is preferably formed using an aerosol jet coating process, wherein at least partially dried to cure the sublayer structure prior to printing the top layer structure. Multilayer printed electronic devices have been shown by aerosol jet printing in ACS (ACS Appl. Mater. Interfaces 2014, 6 18704-18711).

[0175] Effective conditions for forming a hardened coating on at least a portion of a substrate using a liquid-jet or aerosol-jet coating composition preferably include applying thermal energy (e.g., using a convection oven or induction coil), UV radiation, IR radiation, or electron beam radiation to the liquid-jet or aerosol-jet coating composition. Such processes can be performed in one or more discrete or combined steps. These conditions may include applying thermal energy. Applying thermal energy may include using an oven temperature of at least 100°C or at least 177°C. Applying thermal energy may further include using an oven temperature of up to 300°C or up to 250°C. Applying thermal energy may include heating the coated substrate to a peak metallization temperature (PMT) of at least 177°C over a suitable time period. Preferably, applying thermal energy includes heating the coated substrate to a peak metallization temperature (PMT) of at least 218°C over a suitable time period. The time period may be as short as 5 seconds or as long as 15 minutes, and preferably less than one minute, for forming a roll-to-roll coating. Ideally, this occurs in a continuous process.

[0176] The coating method using a water-based dispersion in a liquid jet or aerosol jet system for manufacturing metal packages disclosed herein can be adapted from known inkjet printing, such as those described in the following documents: U.S. Patent No. 7,279,506 (Sisler et al.), U.S. Patent No. 9,428,663 (Song et al.), U.S. Patent Publication No. 2008 / 0062381 (Doshi et al.), and U.S. Patent Publication No. 1004 / 5938 (Doshi).

[0177] Generally, liquid jet coating uses an array of small liquid jets controlled by individual piezoelectric valves that open or close the flow of the coating composition. Typically, the jets are directed at the surface to be coated, and the piezoelectric valves are controlled by a computer that can print a single film or pattern based on the operator's needs. With this type of application process, the coating remains in liquid form upon contact with the substrate.

[0178] Generally, aerosol jet coating converts a liquid coating composition into an aerosol, for example, using ultrasonic energy. The aerosol is pneumatically accelerated through a tube and ultimately transferred to the substrate via a small nozzle. Significant evaporation occurs during this process, and the coating is largely solid when it contacts the substrate.

[0179] Both liquid jet coating and aerosol jet coating methods offer significant improvements over conventional roller or spray coating methods for substrate application. Methods for coating substrates using liquid jet coating.

[0180] A general schematic diagram of an exemplary liquid jet coating system is shown in Figure 1. Arrow (1) indicates the flow direction of an aqueous dispersion from a holding tank (not shown). A piezoelectric diaphragm (2) controls the flow of the aqueous dispersion through a nozzle (3), which is the point of contraction for generating droplets (4). The newly generated droplets (4) then move toward a substrate to be coated (5). After the droplets (4) are applied to the substrate (5), they flow out or wet the substrate, thereby forming part of a liquid jet applied coating (6).

[0181] Drop-on-Demand (DoD) printheads typically contain multiple nozzles (usually 100 to 1000, however professional printheads may contain only a single nozzle), and instead of droplet ejection generated by external fluid pressure as in CIJ printing, the kinetic energy of the droplets comes from a source located very close to each nozzle within the printhead.

[0182] The DoD extrusion mode printhead is composed of a hollow tube of piezoelectric material controlled by an electrical signal. A voltage is applied to the piezoelectric electrodes, causing them to contract, extruding a chamber containing a water-based dispersion, and forcing droplets to be ejected from the nozzle.

[0183] The DoD bending mode printhead consists of a piezoelectric disk mounted on one side of the ink chamber. A pulsed electrical signal causes one side of the chamber to bend inward, reducing the volume of the chamber. This sudden reduction in volume generates the pulsed pressure required to eject the droplet from the nozzle.

[0184] The DoD push-die piezoelectric printhead has a piezoelectric rod placed near the nozzle portion of the chamber. A pulsed electrical signal causes the piezoelectric rod to expand, thereby extruding ink droplets.

[0185] A DoD shear-mode printhead can also be used. The shear-mode printhead is designed so that shear deformation in the piezoelectric element deforms the upper half of the channel. This deformation occurs in the lower half of the channel, forcing the channel into a V-shape. The channel deflection induces droplet ejection. This is further described in Circuit World 2012, Vol. 38, 4, 193-213.

[0186] For this purpose, many printhead designs utilize the deformation of piezoelectric ceramic elements, while in other types (thermal inkjet printheads), the pressure pulse of the ejected droplets is generated by the expansion of small vapor bubbles, which are generated by the action of small electrically heated elements on the liquid itself. Both types of actuation have advantages and disadvantages. Compared to thermal printheads (which are limited to handling fluids that will evaporate as required), piezoelectric printheads can handle a wider range of liquids, and thermal printheads are simpler and cheaper to manufacture. This is further described in Intl. J. Pharm. 2015, 494, 554-567. Method for coating metal substrates using aerosol jet coating.

[0187] Figure 2 shows a general schematic diagram of an exemplary aerosol jet coating system using the Venturi effect. Arrow (7) indicates the flow direction of the carrier gas used to drive the Venturi mechanism. At region (8), the crossflow of the carrier gas creates a vacuum that draws in the water-based dispersion located in the reservoir (12). Turbulence at this intersection generates aerosol of the water-based dispersion. Arrow (9) indicates the direction in which small aerosol droplets flow out of the reservoir (15). The aerosol droplets contact a virtual impactor (10) that causes the aerosol to condense. Arrow (11) indicates the direction of excess vapor discharge that generates condensed aerosol. Arrow (14) indicates the direction in which the condensed aerosol flows toward a nozzle (not shown) to be applied to the substrate. Large condensed droplets of aerosol contact the wall (13) of the reservoir (12) and return to the bulk water-based dispersion by gravity.

[0188] Pneumatic atomization (Venturi effect) technology can be used to generate aerosols to allow the deposition of high-viscosity liquids (up to 1000 cps). This is described in Int. J. Adv. Manuf Technol. 2019, 105, 4599-4619.

[0189] Figure 3 illustrates a general schematic diagram of exemplary ultrasonic energy using the Venturi effect. In this method, ultrasonic atomization is used to generate droplets of an aqueous dispersion. Arrow (15) indicates the flow direction of the carrier gas in contact with the aerosol droplets (17). Aerosol droplets are formed by ultrasonically treating the aqueous dispersion (18) using an ultrasonic transducer (19). Arrow (16) indicates the direction in which the generated aerosol droplets flow toward a nozzle (not shown) for application to a substrate. Further details of this system and its operation are described in U.S. Patent Publication No. 2005 / 0156991 (Renn).

[0190] In methods using ultrasonic energy, rapid solvent evaporation occurs due to the micron-sized droplets, leading to a reduction in droplet size. A carrier gas (referred to herein as aerosol gas) transports the droplets to the deposition head (i.e., the nozzle). During transport, two mechanisms can result in gravitational settling losses and impacts on the tube wall caused by diffusion. Within the deposition head, the sheath gas surrounds the aerosol.

[0191] Gas, collimated beam. As the droplet passes through the deposition head or nozzle, it may deviate from its flow path due to inertial effects within the narrow converging nozzle, resulting in aerodynamic focusing. Finally, the droplet can be guided toward the substrate in an impinging jet. This process is further described in Ind. Eng. Chem. Res. 2015, 54, 769-779.

[0192] A general schematic diagram of an exemplary aerosol jet coating deposition head or nozzle is shown in Figure 4. Arrow (20) indicates the flow direction of condensed aerosol from the reservoir via ultrasonic treatment / pneumatic atomization. Sheath gas (21) (such as dry N2 (HP grade, 99.998%)) accelerates and focuses the condensed aerosol into an airflow (23) toward the substrate (22) to be coated. Sheath gas ensures that the aerosol does not contact the nozzle wall, thereby reducing nozzle fouling and clogging. After the aerosol flow (23) is applied to the substrate (22), it condenses on the substrate, thereby forming part of the coating (24) applied by aerosol jet.

[0193] In some embodiments of the methods disclosed herein, a multi-head device, as described in U.S. Patent No. 10,328,680 (Pervan), may be used. Articles and Methods of Manufacturing

[0194] This disclosure also provides articles including coated substrates as described herein.

[0195] A method of manufacturing a substrate may include: providing a metal substrate (e.g., a roll or sheet) having a hardened, continuously adhesive coating disposed on at least a portion of its surface, wherein: the substrate has an average thickness of at most 0.025 inches; the hardened, continuously adhesive coating is formed from a liquid-jet or aerosol-jet coating composition; wherein the liquid-jet or aerosol-jet coating composition comprises: polymer particles comprising a polymer with an average molecular weight of at least 2000 Daltons, wherein the polymer particles have a particle size distribution with a D50 of less than 10 micrometers; and forming the substrate (e.g., by stamping) into an article. Exemplary Example Example A: Liquid-jet or aerosol-jet coating composition

[0196] Example A-1 is a liquid spray or aerosol spray coating composition for a metal package (e.g., food, beverage, aerosol, or general packaged container (e.g., can, cup), part thereof, or metal closure), comprising: polymer particles comprising a polymer with an average molecular weight of at least 2000 Daltons, wherein the polymer particles have a particle size distribution with a D50 of less than 10 micrometers; and a liquid carrier comprising water comprising the majority amount of the liquid carrier.

[0197] Example A-2 is the liquid spray or aerosol spray coating composition of Example A-1, wherein the polymer particles have a particle size distribution with a D50 of less than 5 micrometers, less than 1 micrometer, or less than 0.5 micrometers.

[0198] Example A-3 is a liquid spray or aerosol spray coating composition of Example A-1 or A-2, wherein the polymer particles have a particle size distribution with D90 of less than 10 micrometers, less than 5 micrometers, less than 1 micrometer or less than 0.5 micrometers.

[0199] Examples A-4 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles have a particle size distribution with a D95 of less than 10 micrometers, less than 5 micrometers, less than 1 micrometer, or less than 0.5 micrometers.

[0200] Examples A-5 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles have a particle size distribution with a D99 of less than 10 micrometers, less than 5 micrometers, less than 1 micrometer, or less than 0.5 micrometers.

[0201] Examples A-6 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles have a particle size distribution with a D50 (preferably D90, D95 or D99) of at least 0.01 micrometers, at least 0.05 micrometers or at least 0.1 micrometers.

[0202] Examples A-7 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing embodiments, wherein the solid content of the coating composition (before being incorporated into the liquid-jet or aerosol-jet coating system) is at least 10 wt-%, at least 15 wt-%, or at least 20 wt-%.

[0203] Examples A-8 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, wherein the solid content of the coating composition (before being incorporated into the liquid-jet or aerosol-jet coating system) is at most 50 wt-%, at most 40 wt-%, or at most 30 wt-%.

[0204] Examples A-9 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, comprising at least 30 wt%, at least 50 wt%, or at least 70 wt% of the polymer particles based on the total solids content of the coating composition (i.e., the total weight of the total hardened coating).

[0205] Example A-10 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, which contains at most 99 wt%, at most 97 wt%, or at most 95 wt% of the polymer particles based on the total solids content of the coating composition (i.e., the total weight of the total hardened coating).

[0206] Example A-11 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the viscosity of the coating composition used in the liquid spray application process is preferably at least 1 centipoise (cps), at least 10 cps, or at least 20 cps.

[0207] Example A-12 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the viscosity of the coating composition used in the liquid spray application process is preferably at most 50 centipoise (cps), at most 40 cps, or at most 30 cps.

[0208] Example A-13 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the viscosity of the coating composition used in the aerosol spray application process is preferably at least 1 centipoise (cps), at least 50 cps, or at least 100 cps.

[0209] Example A-14 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the viscosity of the coating composition used in the aerosol spray application process is preferably at most 1,000 centipoise (cps), at most 500 cps, or at most 200 cps.

[0210] Example A-15 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the surface tension of the coating composition used in the liquid or aerosol spray application process is at least 10 millinewtons / meter (mN / m), at least 20 mN / m, or at least 30 nM / m.

[0211] Example A-16 is a liquid-jet or aerosol-jet coating composition as described in any of the foregoing examples, wherein the surface tension of the coating composition used in the liquid or aerosol-jet application process is at most 50 millinewtons / meter (mN / m), at most 45 mN / m, or at most 40 mN / m.

[0212] Example A-17 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the polymer particles comprise thermoplastic polymers.

[0213] Example A-18 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the polymer particles comprise polymers with a melt flow index greater than 15 g / 10 min, greater than 50 g / 10 min, or greater than 100 g / 10 min.

[0214] Example A-19 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the polymer particles contain a polymer with a melt flow index of up to 200 g / 10 min or up to 150 g / 10 min.

[0215] Examples A-20 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles comprise thermosetting polymers.

[0216] Example A-21 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the polymer particles comprise an amorphous polymer with a glass transition temperature (Tg) of 15°C, at least 20°C, or at least 25°C.

[0217] Example A-22 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the polymer particles comprise an amorphous polymer with a Tg of up to 150°C, up to 125°C, up to 110°C, up to 100°C, up to 80°C, or up to 50°C.

[0218] Examples A-23 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles comprise crystalline or semi-crystalline polymers with a melting point of at least 40°C.

[0219] Examples A-24 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the polymer particles comprise crystalline or semi-crystalline polymers with a melting point of up to 130°C.

[0220] Examples A-25 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, wherein the polymer particles comprise polymers selected from polyacrylic acid, polyether, polyolefin, polyester, polyurethane, polycarbonate, polystyrene, or combinations thereof (i.e., copolymers or mixtures thereof, such as polyether-acrylate copolymers). Preferably, the polymer is selected from polyacrylic acid, polyether, polyolefin, polyester, or combinations thereof.

[0221] Examples A-26 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, wherein the Mn of the polymer is at least, at least 3,000 Daltons, or at least 4,000 Daltons.

[0222] Example A-27 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, wherein the Mn of the polymer is up to 60,000 Daltons.

[0223] Example A-28 is a liquid jet or aerosol inkjet coating composition as in Example A-27, wherein the Mn of the polymer is up to 40,000 Daltons or up to 20,000 Daltons.

[0224] Examples A-29 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, wherein the polymer has a polydispersity index (Mw / Mn) of less than 4, less than 3, less than 2, or less than 1.5.

[0225] Examples A-30 are liquid spray or aerosol spray coating compositions as described in any of the foregoing examples, further comprising one or more selected from lubricants, tackifiers, crosslinking agents, catalysts, colorants (e.g., pigments or dyes), ferromagnetic particles, degassing agents, leveling agents, wetting agents, surfactants, flow control agents, heat stabilizers, corrosion inhibitors, tackifiers, inorganic fillers, and combinations thereof.

[0226] Example A-31 is a liquid spray or aerosol spray coating composition as in Example A-30, which further includes one or more colorants.

[0227] Example A-32 is a liquid-jet or aerosol-jet coating composition as in Example A-31, wherein the one or more colorants are present in the liquid-jet or aerosol-jet coating composition in an amount of at least 1 wt-%, at least 2 wt-%, at least 5 wt-%, at least 10 wt-%, or at least 15 wt-%, based on the total solids content of the coating composition (i.e., the total weight of the overall hardened coating).

[0228] Example A-33 is a liquid-jet or aerosol-jet coating composition as in Example A-31 or A-32, wherein the one or more colorants are present in the liquid-jet or aerosol-jet coating composition in an amount of up to 50 wt%, up to 40 wt%, up to 30 wt%, or up to 20% of the total solids content of the coating composition (i.e., the total weight of the total hardened coating).

[0229] Example A-34 is a liquid spray or aerosol spray coating composition as in any of Examples A-30 to A-33, further comprising one or more lubricants.

[0230] Example A-35 is a liquid-jet or aerosol-jet coating composition as in Example A-34, wherein the one or more lubricants are present in the liquid-jet or aerosol-jet coating composition in an amount of at least 0.1 wt%, at least 0.5 wt%, or at least 1 wt%, based on the total solids content of the coating composition (i.e., the total weight of the overall hardened coating).

[0231] Example A-36 is a liquid-jet or aerosol-jet coating composition as in Example A-34 or A-35, wherein the one or more lubricants are present in the liquid-jet or aerosol-jet coating composition in an amount of up to 4 wt%, up to 3 wt%, or up to 2 wt%, based on the total solids content of the coating composition (i.e., the total weight of the total hardened coating).

[0232] Example A-37 is a liquid spray or aerosol spray coating composition as in any of Examples A-30 to A-36, further comprising one or more crosslinking agents and / or catalysts.

[0233] Examples A-38 are liquid spray or aerosol spray coating compositions as described in any of the foregoing embodiments, which substantially do not contain bisphenol A, bisphenol F, and bisphenol S, structural units derived therefrom, or both.

[0234] Examples A-39 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, and substantially do not contain all bisphenol compounds, structural units derived therefrom, or both, except for TMBPF.

[0235] Example A-40 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, which, when tested according to the global extraction test, forms a coating containing less than 50 ppm, less than 25 ppm, less than 10 ppm, or less than 1 ppm of extractable material (if present).

[0236] Example A-41 is a liquid spray or aerosol spray coating composition as described in any of the foregoing examples, which forms a coating that is adhered to a substrate (such as a metal substrate) according to an adhesion test, and has an adhesion rating of 9 or 10, preferably 10.

[0237] Examples A-42 are liquid-jet or aerosol-jet coating compositions as described in any of the foregoing examples, forming a continuous, hardened coating free from pinholes and other coating defects that would expose the substrate. Such film defects / failures can be indicated by a current measured in milliamperes (mA) using the plate continuity test described in the use examples section.

[0238] Examples A-43 are liquid-jet or aerosol-jet coating compositions as described in any of the preceding examples. When applied to a cleaned and pretreated aluminum plate and cured and baked for an appropriate duration to achieve a peak metal temperature (PMT) of 242°C and a dry film thickness of approximately 7.5 mg / m², and forming a fully converted 202 standard beverage can end, when exposed to an electrolyte solution containing 1% by weight NaCl dissolved in deionized water for 4 seconds, a current of less than 5 mA is passed. Example B: Method for coating a metal substrate and the coated metal substrate

[0239] Example B-1 is a method of coating a metal substrate suitable for forming a metal package (e.g., food, beverage, aerosol, or general packaging container (e.g., can), a portion thereof, or a metal closure), the method comprising: providing a liquid jet or aerosol jet coating composition for metal packaging as in any of Example A; guiding the liquid jet or aerosol jet coating composition to at least a portion of the metal substrate; and providing effective conditions for forming a hardened, continuously adhered coating on at least a portion of the metal substrate by the liquid jet or aerosol jet coating composition.

[0240] Example B-2 is a method of coating a metal substrate suitable for forming a metal package (e.g., a food, beverage, aerosol, or general packaging container (e.g., a can), a portion thereof, or a metal closure), the method comprising: providing a metal substrate; providing a liquid jet or aerosol jet coating composition for metal packaging as in any of Example A; selectively applying the liquid jet or aerosol jet coating composition to at least a portion of the metal substrate to form a patterned coating; and providing effective conditions for forming a hardened adhesive patterned coating on at least a portion of the metal substrate by the liquid jet or aerosol jet coating composition.

[0241] Example B-3 is a method of coating a metal substrate suitable for forming a metal package (e.g., a food, beverage, aerosol, or general packaging container (e.g., a can), a portion thereof, or a metal closure), the method comprising: providing a metal substrate; providing a plurality of liquid-jet or aerosol-jet coating compositions for metal packaging as described in any of Example A, wherein at least two of the plurality of liquid-jet or aerosol-jet coating compositions for metal packaging are different; directing each of the plurality of coating compositions to at least a portion of the metal substrate such that at least one coating composition is deposited on another different coating composition (before or after the lower coating composition has hardened to form a coating); and providing effective conditions for the plurality of liquid-jet or aerosol-jet coating compositions to form a hardened, continuously adherent coating on at least a portion of the metal substrate.

[0242] Examples B-4 are methods as described in any of the preceding Examples B, wherein providing effective conditions for forming a hardened coating on at least a portion of a metal substrate by liquid jetting or aerosol jetting coating composition includes applying thermal energy (e.g., using a convection oven or induction coil), UV radiation, IR radiation, or electron beam radiation to the powder coating composition.

[0243] Example B-5 is the method of Example B-4, wherein providing conditions includes applying heat energy.

[0244] Example B-6 is the method of Example B-5, wherein applying heat energy includes applying heat energy at a temperature of at least 100°C or at least 177°C.

[0245] Example B-7 is the method of any one of Examples B-5 or B-6, wherein applying heat energy includes applying heat energy at a temperature of up to 300°C or up to 250°C.

[0246] Examples B-8 are methods of any one of the preceding Examples B, wherein the metal substrate comprises steel, stainless steel, tin-free steel (TFS), tin-plated steel, electrolytic tin plate (ETP), or aluminum.

[0247] Examples B-9 are methods as described in any of the preceding Examples B, wherein the metal substrate is a low-temperature cleaned metal substrate.

[0248] Example B-10 is a method as described in any of the preceding Examples B, which further includes performing a low-temperature cleaning of the metal substrate before each of the plurality of powder coating compositions is directed to at least a portion of the metal substrate.

[0249] Example B-11 is a method as described in any of the preceding Examples B, wherein the metal substrate has an average thickness of up to 635 micrometers (or up to 375 micrometers).

[0250] Example B-12 is the method of any of the aforementioned Example B, wherein the metal substrate has an average thickness of at least 125 micrometers.

[0251] Example B-13 is a method as described in any of the preceding Examples B, wherein the hardened adhesive coating has an average thickness of up to 100 micrometers or a maximum thickness of up to 100 micrometers.

[0252] Example B-14 is the method of Example B-13, wherein the hardened adhesive coating has an average thickness of up to 50 micrometers, preferably up to 25 micrometers (e.g., up to 20 micrometers, up to 15 micrometers, up to 10 micrometers, or up to 5 micrometers).

[0253] Example B-15 is the method of any of the preceding Example B, wherein the hardened adhesive coating has an average thickness of at least 1 micrometer (or at least 2 micrometers, at least 3 micrometers or at least 4 micrometers).

[0254] Example B-16 is a coated metal substrate having a surface at least partially coated with a coating prepared by any of the methods described in Example B above.

[0255] Example B-17 is a coated metal substrate as in Example B-16, wherein the substrate is a stretched and restretched substrate.

[0256] Example B-18 is a coated metal substrate as in Example B-16, wherein the metal substrate is a sheet material.

[0257] Example B-19 is a coated metal substrate of Example B-16, wherein the metal substrate is used to manufacture aluminum coils for beverage can ends (where a hardened coating is applied to the inner or outer surface of the beverage can end, or both). Example C: Metal Encapsulation and Manufacturing Method

[0258] Example C-1 is a metal package (e.g., a food, beverage, aerosol, or general package container (e.g., a can or cup), a portion thereof, a metal closure, or a pull tab for an easy open end), which includes a metal substrate having a surface at least partially coated with a coating prepared by any one of Examples B-1 to B-15.

[0259] Example C-2 is a metal package as in Example C-1, wherein the surface is the inner surface, outer surface, or both of the container (e.g., can or cup) body.

[0260] Example C-3 is a metal package as in Example C-1 or C-2, wherein the surface is a riveted can end and / or a pull tab surface.

[0261] Example C-4 is a metal package as described in any one of Examples C-1 to C-3, which is filled with food, beverage or aerosol products.

[0262] Example C-5 is a method of manufacturing a metal package (e.g., a metal package container, such as a food, beverage, aerosol, or general package container (e.g., a can or cup), a portion thereof, or a metal closure for a container (e.g., a metal can or glass bottle)), comprising: providing a metal substrate (e.g., a roll or sheet) having a hardened, continuously adhered coating disposed on at least a portion thereof as described in Examples B-16 to B-19; and forming the substrate (e.g., by stamping) into at least a portion thereof, or a portion thereof, of a metal package container (e.g., a food, beverage, aerosol, or general package container), or a metal closure for a container (e.g., a metal can or glass bottle).

[0263] Example C-6 is a method of manufacturing a metal package (e.g., a metal packaged container, such as a food, beverage, aerosol, or general packaged container (e.g., a jar or cup), a portion thereof, or a metal closure such as for a metal packaged container or glass jar) in one location and / or in a continuous manufacturing line or process, the method comprising: providing a metal substrate; providing a liquid-jet or aerosol-jet coating composition for metal packaging as in any of Example A; directing the liquid-jet or aerosol-jet coating composition to at least a portion of the metal substrate; providing effective conditions for the coating composition to form a hardened, continuously adhered coating on at least a portion of the metal substrate; and forming the at least partially coated metal substrate into at least a portion of, a portion thereof, or a metal closure (e.g., for a metal packaged container or glass jar) of a metal packaging container (e.g., a food, beverage, aerosol, or general packaged container (e.g., a jar or cup)). Example

[0264] These examples are for illustrative purposes only and are not intended to unduly limit the scope of the accompanying embodiments. Although the numerical ranges and parameters illustrating the broad scope of this disclosure are approximate, the numerical values ​​described in the specific examples are stated as precisely as possible. However, any numerical value inherently contains certain errors, which necessarily arise from the standard deviation found in its respective test measurements. At least, and without attempt to limit the application of the equivalence principle to the scope of the embodiments, each numerical parameter should be interpreted at least according to the number of significant figures stated and by applying common rounding techniques.

[0265] Unless otherwise stated, all parts, percentages, ratios, etc., in the examples and the remainder of the instructions are by weight, and all reagents used in the examples are obtained or available from general chemical suppliers such as Sigma-Aldrich Company, Saint Louis, Missouri, or can be synthesized by known methods. The following abbreviations may be used in the following examples: ppm = parts per million; phr = parts per hundred parts of rubber; mL = milliliter; L = liter; m = meter; mm = millimeter; cm = centimeter; kg = kilogram; g = gram; min = minute; s = second; hrs = hour; ℃ = degree Celsius; ℉ = degree Fahrenheit; MPa = megapascal; and Nm = newton-meter; Mn = number average molecular weight; cP = centipoise. Test Methods

[0266] Unless otherwise instructed, the following test method may be used. Adhesion test

[0267] According to ASTM D 3359-17 (2017) Test Method B, for coatings ≤ 125 micrometers thick, an adhesion test is performed using SCOTCH 610 tape (available from 3M in Saint Paul, MN) and a grid pattern consisting of 4 transverse scratches and 4 longitudinal scratches (approximately 1 to 2 mm apart). The test is typically repeated 3 times per sample. Adhesion is rated on a scale of 0 to 10, where a "10" indicates no adhesion failure, a "9" indicates 90% adhesion retention, an "8" indicates 80% adhesion retention, and so on. Commercially available reactive coatings typically require an adhesion rating of 9 or 10. Therefore, in this document, an adhesion rating of 9 or 10, preferably 10, is considered adhesion. Differential scanning calorimetry for Tg

[0268] The total hardened coating sample for differential scanning calorimetry ("DSC") testing was weighed into a standard sample pan and analyzed using the standard DSC thermal cooling method. The sample was equilibrated at -60°C, then heated to 200°C at 20°C / min, cooled to -60°C, and subsequently reheated to 200°C at 20°C / min. The glass transfer temperature was calculated from the thermal analysis curve of the last thermal cycle. Glass transfer was measured at the inflection point of the transfer. Molecular weight determination was performed by gel permeation chromatography.

[0269] Samples used for gel permeation chromatography (“GPC”) testing are prepared by first dissolving a total hardened coating in a suitable solvent (e.g., THF if applicable to a given total hardened coating). Aliquots of this solution are then analyzed using a mixture of GPC and polystyrene (“PS”) standards. After processing the GPC run and validating the standards, the molecular weight of the sample is calculated. Whole-domain extraction test.

[0270] The total extraction test is designed to assess the amount of mobile material that may potentially migrate out of a coating and into food packaged in a coated container. Generally, the coated substrate is subjected to water or solvent mixtures under various conditions to simulate a given end use.

[0271] Acceptable extraction conditions and media are described in 21 CFR §175.300, paragraphs (d) and (e). The extraction procedures used in this disclosure were performed in accordance with the Food and Drug Administration (FDA) "Preparation of Premarket Submission for Food Contact Substances: Chemistry Recommendations," (December 2007). The permissible whole-field extraction limit is 50 parts per million (ppm) as defined by FDA rules.

[0272] The single-sided extraction cell was designed with minor modifications according to the design described in the Journal of the Association of Official Analytical Chemists, 47(2):387(1964). The cell measures 9 in × 9 in × 0.5 in, with a 6 in × 6 in opening at the center of the TEFLON spacer. This allows test articles of 36 in² or 72 in² to be exposed to a food-simulated solvent. The cell holds 300 mL of food-simulated solvent. When exposed to test articles of 36 in² and 72 in², the solvent-to-surface-area ratios are 8.33 mL / in² and 4.16 mL / in², respectively.

[0273] For the purposes of this disclosure, the test articles consisted of 0.0082-inch thick 5182 aluminum alloy plates pretreated with Permatreat® 1903 (supplied by Chemetall GmbH, Frankfurt am Main, Germany). These plates were coated with a test coating (completely covering at least 6 in × 6 in area required for assembling the test cell) to achieve a final dry film thickness of 11 g / m² after a 10-second curing bake, resulting in a peak metallographic temperature (PMT) of 242°C. Two test articles were used per cell, with a total surface area of ​​72 in² for each cell. The test articles were extracted four times using 10% aqueous ethanol as a food simulant. The test articles were treated at 121°C for two hours and then stored at 40°C for 238 hours. Samples of the test solution were taken after 2, 24, 96, and 240 hours. The test articles were extracted four times using 10% aqueous ethanol under the conditions listed above.

[0274] Each test solution was evaporated to dryness by heating it on a hot plate in a pre-weighed 50 mL beaker. Each beaker was dried in an oven at 250℉ (121℃) for at least 30 minutes. The beakers were then placed in a desiccator to cool and weighed to constant weight. Constant weight was defined as three consecutive weighings with a difference of no more than 0.00005 g.

[0275] Solvent blanks using PTFE sheets in the extraction cell were also exposed to the simulants and evaporated to constant weight to correct for the weight of the extraction residues of the test items by means of the extraction residues added by the solvent itself. Two solvent blanks were extracted at each time point, and the average weight was used for correction.

[0276] Total nonvolatile extractables are calculated as follows: Where: Ex = Extraction residue (mg / in2) e = Extraction residue from each repeated test (mg) s = Extraction area (in2)

[0277] A superior coating yields global extraction results of less than 50 ppm, even better results of less than 10 ppm, and still better results of less than 1 ppm. Ideally, the global extraction result is undetectable. Plate continuity test.

[0278] This test measures the continuity of a coating applied to a flat metal substrate and indicates the presence or absence of a continuous film that is largely free of pores, cracks, or other defects that could expose the metal substrate. This method can be used in the laboratory and on commercially available coated steel and aluminum substrates. The test assembly comprises: a non-conductive, solid substrate (large enough to support the test plate); a hinged clamping mechanism mounted to the substrate; a non-conductive electrolyte reservoir connected to the clamping mechanism in a manner that allows it to be lowered and sealed onto the test plate (resulting in a 6-inch diameter circular area on the test plate being exposed to the electrolyte); an orifice in the electrolyte reservoir, large enough to fill the reservoir with electrolyte; and electrodes inserted into the electrolyte reservoir. A WACO Enamel Rater II (available from Wilkens-Anderson Company, Chicago, IL) with an output voltage of 6.3 volts is used in conjunction with the test assembly (described below) to measure metal exposure in the form of current. The electrolyte solution used in the following tests consists of 1% by weight sodium chloride dissolved in deionized water.

[0279] Apply and cure an 8-inch by 8-inch metal plate with the coating to be tested, according to the formula or technical data sheet. If no coating thickness or curing schedule is specified for the test coating, the test plate should be coated with a curing bake of appropriate duration to achieve a final dry film thickness of 11 g / m² (gsm) to reach a peak metal temperature (PMT) of 242°C. Each test plate may be used only once and should not be visibly scratched or stretched. Place the test plate in the test assembly with the coated side facing up. Then lower the electrolyte reservoir onto the test plate and lock it in place using the closing clamp. The edge of the panel in the uncoated area connected to the positive lead from the enamel grader. A small area may need to be sanded or scraped to expose the bare metal substrate. Then fill the electrolyte cell with sufficient electrolyte solution to ensure contact with the negative terminal of the cell. The negative lead from the enamel grader is connected to the negative terminal on top of the cell. Finally, lower the probes on the Waco enamel grader to activate the test current.

[0280] Membrane defects / faults will be represented by current measured in milliamperes (mA). Record the initial milliampere reading for each test plate, and state the results in milliamperes. If more than one determination is made for each variable, record the average reading.

[0281] For the purposes of this application, when evaluated according to this test, the continuous coating will pass a current of less than 200 mA. According to this test, the preferred coating disclosed herein passes a current of less than 100 mA, more preferably less than 50 mA, less than 10 mA or less than 5 mA, most preferably less than 2 mA and most preferably less than 1 mA. Flexibility Test

[0282] This test measures the ability of a coated substrate to maintain its integrity as it undergoes the forming process required to create an article (such as a riveted beverage can end). It is a measure of whether cracks or breaks exist in the formed can end. The can end is typically placed on a cup filled with an electrolyte solution. The cup is inverted so that the surface of the can end is exposed to the electrolyte solution. The current intensity passing through the can end is then measured. If the coating remains intact (without cracks or breaks) after manufacturing, a minimum current will pass through the can end.

[0283] For this assessment, the fully converted 202 standard open beverage end was exposed to a room temperature electrolyte solution containing 1% by weight NaCl in deionized water for 4 seconds. The coating to be assessed was present on the inner surface of the beverage end with a dry film thickness of 6 to 7.5 mg / m² ("msi") (or 9.3 to 11.6 g / m²), where 7 msi is the target thickness, and had been cured according to the formula or data sheet. If no curing schedule is specified for the test coating, the test plate was coated using a curing bake of appropriate duration to achieve a peak metal temperature (PMT) of 242°C. Metal exposure was measured using a WACO Enamel Rater II (available from Wilkens-Anderson Company, Chicago, IL) with an output voltage of 6.3 volts. The measured current intensity was recorded in milliamperes (mA). Can-end continuity was generally tested at the beginning and then after pasteurization, Dowfax, or distillation of the can end.

[0284] If the coating of this disclosure carries a current of less than 200 mA, it initially "passes" the test. According to the test, the preferred coating of this disclosure initially carries a current of less than 100 mA, more preferably less than 50 mA, less than 10 mA or less than 5 mA, most preferably less than 2 mA and most preferably less than 1 mA.

[0285] After pasteurization, Dowfax detergent testing, or distillation, the preferred coating exhibits a continuity of less than 20 mA, more preferably less than 10 mA, even more preferably less than 5 mA, and even more preferably less than 1 mA. Weather resistance

[0286] This test is generally conducted using an unfiltered weathering tester, preferably a carbon arc unfiltered weathering tester, in which the coating is exposed to unfiltered UV radiation for a fixed period of time (e.g., 500 hours, 1000 hours, etc.) to simulate years of direct exposure to sunlight, and under conditions more demanding than conventional accelerated climate tests (such as QUV tests). Without being theoretically limited, combinations of glass flake additives of specific particle sizes and optimal thicknesses of the second coating can be combined to provide a weather-resistant coating. In one sample, when subjected to 1000 hours of weathering testing, the coating composition described herein provides weather resistance comparable to or even superior to conventional coatings. Detergent resistance

[0287] Detergent resistance can be determined using tests such as (ASTM DD2248 or its modifications). Water resistance

[0288] Water resistance can be determined using tests such as (ASTM D870 or its modifications). Corrosion resistance

[0289] For example, corrosion resistance can be determined using tests (such as Appendix 5 of ASTM G85 or its modifications).

[0290] All disclosures of the patents, patent documents, and publications cited herein are incorporated herein by reference in their entirety as if each were individually incorporated. In the event of any conflict or discrepancy between this specification and the disclosures in any document incorporated herein by reference, this specification shall prevail. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein, and such examples and examples are presented by way of example only, and the scope of this disclosure is limited only by the embodiments set forth herein. [Simplified Explanation of the Diagram]

[0036] [Figure 1] is a schematic diagram of an exemplary liquid jet application system. [Figure 2] is a schematic diagram of an exemplary aerosol jet application system using the Venturi effect. [Figure 3] is a schematic diagram of an exemplary aerosol jet application system using ultrasonic energy. [Figure 4] is a schematic diagram of an exemplary nozzle used in an aerosol jet application system.

Claims

1. A method of coating a roll metal substrate, the method comprising: providing a liquid-jet or aerosol-jet coating composition comprising: polymer particles comprising a polymer with a number average molecular weight of at least 2000 Daltons, wherein the polymer particles have a particle size distribution with a D50 of less than 10 micrometers; and a liquid carrier comprising water comprising a major amount of the liquid carrier; directing the liquid-jet or aerosol-jet coating composition to at least a portion of the roll metal substrate, wherein the roll metal substrate has a thickness of 0.010 inches to 0.025 inches; and providing effective conditions for forming a hardened, continuously adhered, weather-resistant coating on at least a portion of the roll metal substrate, thereby forming a coated roll metal substrate.

2. The method of claim 1, wherein the coil metal substrate comprises aluminum, iron, copper, tin, steel, alloys thereof, or combinations thereof.

3. The method of claim 1, wherein the polymer particles have a particle size distribution of D50 less than 5 micrometers, less than 1 micrometer, or less than 0.5 micrometers, and optionally wherein the polymer particles have a particle size distribution of D90 less than 10 micrometers, less than 5 micrometers, less than 1 micrometer, or less than 0.5 micrometers.

4. The method of claim 1, wherein the polymer particles comprise a thermoplastic polymer, optionally wherein the polymer particles comprise a polymer selected from polyacrylic acid (e.g., solution-polymerized acrylic polymers, emulsion-polymerized acrylic polymers, or combinations thereof), polyether, polyolefin, polyester, polyurethane, polycarbonate, polystyrene, or combinations thereof (i.e., copolymers or mixtures thereof, such as polyether-acrylate copolymers), preferably wherein the polymer is selected from polyacrylic acid, polyether, polyolefin, polyester, or combinations thereof.

5. The method of claim 1, wherein the guiding step comprises selectively applying the liquid-jet or aerosol-jet coating composition to at least a portion of the metal substrate to form a patterned coating.

6. The method of claim 1, further comprising providing a plurality of liquid-jet or aerosol-jet coating compositions, wherein at least two of the plurality of liquid-jet or aerosol-jet coating compositions are different, and wherein at least one coating composition is deposited on another different coating composition (before or after the underlying coating composition has hardened to form a coating).

7. A coated coil metal substrate comprising a coil metal substrate having a surface at least partially coated with a coating prepared by any one of claims 1 to 3 above, wherein the coating comprises a hardened adhesive weather-resistant coating.

8. The coated coil metal substrate of claim 7, wherein the coil metal substrate has an average thickness of 0.010 inches to 0.025 inches.

9. The coated roll metal substrate of claim 7, wherein the coating has an average thickness of at least 1 micrometer, at least 2 micrometers, at least 3 micrometers or at least 4 micrometers, optionally wherein the coating has an average thickness of at most 100 micrometers, at most 50 micrometers, preferably at most 25 micrometers, at most 20 micrometers, at most 15 micrometers, at most 10 micrometers or at most 5 micrometers.

10. The coated roll metal substrate of claim 7, wherein the substrate is a stretched and restretched substrate.

11. A coated coil metal substrate as claimed in any of claims 7 to 10, wherein the coating comprises two or more layers, optionally including a first layer and a second layer, the first layer comprising a primer layer and the second layer comprising a topcoat layer.

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