CN117858925A

CN117858925A - Coating compositions, methods of using them, and systems containing them

Info

Publication number: CN117858925A
Application number: CN202280057547.8A
Authority: CN
Inventors: C·王; R·E·道翰保格; B·G·彼得鲁斯基; R·J·小克拉里克; B·K·莱利克
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2021-08-13
Filing date: 2022-08-03
Publication date: 2024-04-09

Abstract

The present disclosure relates to coating compositions comprising an organic solvent and having a shear-thinning rheological profile. At high shear rates, the coating composition has a viscosity low enough to flow through the openings in the high efficiency applicator and be applied to a surface. The coating composition exhibits minimal or no sagging when applied to a vertical surface with low or no shear.

Description

Coating compositions, methods of using them, and systems containing them

Cross Reference to Related Applications

The present application claims priority from U.S. provisional application 63/232,761 filed on day 2021, month 8 and day 13 and U.S. provisional application 63/274,167 filed on day 2021, month 11, and entitled "coating compositions, methods of using them, and systems (Coating compositions, methods for using them and systems that include them) containing them," both of which are incorporated herein by reference.

Technical Field

The present disclosure relates generally to coating compositions for application to a substrate, methods of forming a coating, and systems thereof.

Background

The coating compositions can be applied to a variety of substrates to provide color and other visual effects as well as a variety of designs and patterns. For example, the coating may be applied to a vehicle substrate to provide two or more different colors on different portions of the substrate. To form different designs and patterns, masking materials are typically placed on different portions of the substrate and different coating compositions are applied to the substrate in multiple applications.

Disclosure of Invention

The present disclosure describes coating compositions comprising an organic solvent and having a shear-thinning rheological profile. At high shear rates, the coating composition has a viscosity low enough to flow through the openings in the high efficiency applicator and be applied to a surface. The coating composition exhibits minimal or no sagging when applied to a vertical surface with low or no shear.

Detailed Description

Conditions of temperature and pressure are ambient temperature (22 ℃), 45% relative humidity and standard pressure of 101.3kPa (1 atm), unless otherwise indicated.

Unless otherwise indicated, any term that includes parentheses shall alternatively refer to both whole terms (as if there were brackets) and non-bracketed terms, as well as combinations of each choice. Thus, as used herein, the term "(meth) acrylate" and similar terms are intended to include acrylates, methacrylates, and mixtures thereof.

It is to be understood that the present disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Furthermore, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between (and inclusive of) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

All ranges are inclusive and combinable. For example, the term "0.06 to 0.25wt.%, or a range of 0.06 to 0.08 wt.%" will include each of 0.06 to 0.25wt.%, 0.06 to 0.08wt.%, and 0.08 to 0.25 wt.%. Furthermore, when ranges are given, any endpoints of those ranges and/or numbers recited within those ranges may be combined within the scope of the present disclosure.

As used herein, unless explicitly stated otherwise, all numbers such as those expressing values, ranges, amounts or percentages, and the like, may be read as beginning with the word "about (about)" even if the term does not explicitly appear. Plural encompasses singular and vice versa, unless otherwise specified. As used herein, the term "comprising" and similar terms mean "including but not limited to. Similarly, as used herein, the terms "on … …", "applied on … …", "formed on … …", "deposited on … …", "covered" and "provided on … …" mean formed, covered, deposited or provided on … … but not necessarily in contact with a surface. For example, a coating "formed on" a substrate does not preclude the presence of one or more other coatings having the same or different composition located between the formed coating and the substrate.

As used herein, the transitional term "comprising" (and other comparable terms such as "containing" and "comprising") is "open" and open to include unspecified material. Although described as "comprising," it is within the scope of the present disclosure that the terms "consisting essentially of … …" and "consisting of … ….

As used herein, the term "actinic radiation" refers to electromagnetic radiation that can initiate a chemical reaction. Actinic radiation includes, but is not limited to, visible light, ultraviolet (UV) light, infrared (IR), X-rays, and gamma radiation.

As used herein, the term "adhesion promoter" refers to any material that, when included in a composition, enhances the adhesion of a coating composition to a substrate.

As used herein, the term "alkoxy-functional silicone" and similar terms refer to silicones comprising only alkoxy-functional groups —or, where R can be an alkyl group OR an aryl group.

The terms "a" and "an", as used herein, should be interpreted to include "at least one" and "one or more".

As used herein, the term "applicator" refers to any device capable of applying a coating composition to a substrate, and may include, but is not limited to, rollers, brushes, spray tips in fluid communication with a spray nozzle, and high-efficiency applicators.

As used herein, the term "ASTM" refers to publications ASTM International, west Conshohocken, PA.

As used herein, the term "basecoat" refers to a coating that is applied over a primer (another basecoat) and/or directly over a substrate, optionally including components (such as colorants) that affect color and/or provide other visual effects.

As used herein, the term "binder" refers to a compound or mixture of compounds that is used to bind input materials (including pigments, fillers, and the like, if present) in a coating composition and provide adhesion of a coating film to an underlying surface as a continuous film.

As used herein, the term "clear coat" refers to a coating that is at least substantially transparent or completely transparent and may not contain a colorant. The term "substantially transparent" refers to a coating in which the surface outside the coating is at least partially visible to the naked eye when viewed through the coating. The term "completely transparent" refers to a coating in which the surface outside the coating is completely macroscopic when viewed through the coating. The clearcoat layer may be substantially pigment free. Substantially free of pigment may refer to a "colored clear coat" which may be a coating composition comprising less than 3 wt% pigment, such as less than 2 wt%, less than 1 wt%, or 0 wt%, based on total solids.

As used herein, the term "coating" refers to a finished product produced by applying one or more coating compositions to a substrate and forming the coating by curing (as a non-limiting example). The primer layer, basecoat layer or colored coating layer and clearcoat layer may form part of a coating. As used herein, the term "coating" is used to refer to the result of applying one or more coating compositions to a substrate in one or more applications of such one or more coating compositions. As a non-limiting example, a single coating, referred to as a "colored coating" or "top coating," can be used to provide the function of both the basecoat and the clearcoat, and can include the result of two or more applications of the colored coating composition.

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

As used herein, the term "drop" refers to a drop of coating from a precision applicator that is applied far enough apart to reduce the volume of material applied, but close enough to flow together and provide conformal coating coverage.

As used herein, the term "continuous jet" refers to a continuous stream of coating from a precision applicator that is applied to a substrate to provide a line of cutting edges at the end of the applied coating.

As used herein, the term "cross-linked" refers to a bond or a short sequence of bonds that connects one polymer chain to another. "highly crosslinked" refers to the fact that the amount of crosslinking renders the polymer swellable to some extent, but insoluble in solvents or water.

As used herein, the term "crosslinker" refers to a molecule or polymer that contains functional groups that react with crosslinking functional groups of the polymer and/or resin in the coating composition.

As used herein, the term "crosslinking functionality" refers to functionality located in the polymer backbone, often in a side group of the polymer backbone, terminally located on the polymer backbone, or a combination thereof, wherein such functionality is capable of reacting with other crosslinking functionalities or a separate crosslinking agent during curing to produce a crosslinked coating.

As used herein, the terms "curable," "curing," and the like, as used in connection with a coating composition, refer to at least a portion of the components comprising the coating composition being polymerizable and/or crosslinkable upon exposure to higher temperatures or ultraviolet radiation, as non-limiting examples.

As used herein, the terms "droplet" and "droplet" refer to a column of liquid that is entirely defined by a free surface.

As used herein, "drop-on-demand" refers to a precise applicator that controls the volume of a single drop and dispenses that drop only when indicated.

As used herein, the term "drying" refers to the removal of volatile compounds from a film, coating or applied paint.

As used herein, the term "dye" refers to a colored substance, in many cases an organic compound, that can be chemically bonded to a substrate or another component in a coating composition.

As used herein, the term "film-forming" material refers to the film-forming component of a coating composition and may include a polymer, a resin, a crosslinking material, or any combination thereof as the film-forming component of the coating composition. The film-forming material may be dried or cured.

As used herein, the term "flow rate" refers to the volume of coating composition exiting the applicator per unit time, as a non-limiting example in cm ³ /min meter.

As used herein, the term "completely transparent" refers to a coating in which the surface outside the coating is completely macroscopic when viewed through the coating.

As used herein, "high-efficiency applicator" refers to a precision application device that can enable the coating composition to be applied to at least a portion of a substrate without overspray, as a non-limiting example, with a transfer efficiency greater than 85%.

The term "molecular weight" as used herein refers to the weight average molecular weight as determined by Gel Permeation Chromatography (GPC) using appropriate polystyrene standards, unless otherwise indicated. If the number average molecular weight is specified, the weight is determined in the same GPC manner, while the number average is calculated from the polymer molecular weight distribution data thus obtained.

As used herein, the terms "multi-component," "multi-K," and "multi-pack" refer to coating compositions that comprise a first component comprising a crosslinkable resin, a second component comprising a crosslinker, and additional components that may or may not comprise a crosslinkable resin or crosslinker, wherein the components are maintained separately until use. The crosslinkable resin and the crosslinking agent are capable of reacting when combined to form a thermosetting composition. When the multi-component coating composition does not contain additional components, it is a two-component coating composition.

As used herein, the term "nozzle" refers to a component of an applicator having an opening through which a coating composition flows, is ejected or is sprayed, and unless otherwise indicated, the term "nozzle" is used interchangeably with any of a spray valve or a piezo, thermal, acoustic or ultrasonic actuated spray valve or nozzle.

As used herein, "overspray" refers to the portion of the coating composition that does not fall within the target area.

As used herein, the terms "one component", "1-K" and "1-package" refer to coating compositions in which all coating components remain in the same package after manufacture, during transportation and storage. As a non-limiting example, a coating composition is considered a 1-K coating composition even if a solvent is added to the 1-K composition to reduce its viscosity or solids.

As used herein, the term "organic solvent" refers to a carbon-based material that is capable of dissolving or dispersing other materials.

As used herein, the term "overlap" refers to the amount of coating composition in the path width applied over the coating composition of the previous path width.

As used herein, the term "path width" refers to the distance perpendicular to the direction of movement of an applicator applying a coating composition to a substrate.

As used herein, the term "pigment" refers to an organic or inorganic material or combination thereof that may be a colored material, completely or nearly insoluble in a solvent, and may also be functional, non-limiting examples being anti-corrosive pigments or effect pigments, non-limiting examples including mica and aluminum.

As used herein, the prefix "multiple" refers to two or more. As a non-limiting example, polyisocyanate refers to a compound comprising two or more isocyanate groups, and polyol refers to a compound comprising two or more hydroxyl groups.

As used herein, the term "polyisocyanate" refers to blocked (or blocked) polyisocyanates as well as unblocked polyisocyanates.

As used herein, the term "polymer" includes homopolymers (formed from one monomer) as well as copolymers formed from or comprising two or more different monomer reactants. Furthermore, the term "polymer" includes prepolymers and oligomers.

As used herein, the term "primer coating" refers to a base coat that can be applied to a substrate to prepare a surface for application of a protective or decorative coating composition.

As used herein, the term "rheology modifier" refers to a material that alters the rheology or flow properties of the fluid composition to which it is added and may include, but is not limited to, natural gums, synthetic resins, organoclays, hydrogenated castor oils, fumed silica, polyamides, associative thickeners, overbased sulfonates (colloidal calcium sulfonate dispersed in an oil, the excess sulfonate acting as a surfactant, as a non-limiting example), inorganic crystals, non-aqueous microgels, and polyurea compounds insoluble in organic solvents.

As used herein, the term "sagging" refers to downward movement of a coating composition that can occur after application of the coating composition to a substrate and before the coating composition solidifies, cures and/or dries, non-limiting examples include sagging lines, sagging curtains, drooling, or other defects and variations in the coating that result in coating non-smoothness, as tested according to ASTM D4400 (2018). Sagging can be measured in mm using a ruler. A drip or wing-like defect of paint can be seen under the panel aperture. ASTM D4400 suggests a sag limit of 1.6mm (distance between drop lines). As used herein, "sag free" refers to the absence of visible dripping or winged defects, and "minimal sag" refers to the absence of dripping or winged defects between the descent lines of more than 5 mm.

As used herein, the term "shear strain" refers to deformation or flow of a coating composition in response to an applied shear stress.

As used herein, the term "shear stress" refers to the pressure applied to the surface of a coating composition.

As used herein, the term "shear thinning" refers to the non-newtonian behavior of a fluid whose viscosity decreases under increased shear stress.

As used herein, the term "flow" refers to the bulk of a flowing liquid (in many cases, a flowing coating composition).

As used herein, the term "silicone" and similar terms refer to polysiloxane polymers, which are based on structures comprising alternating silicon and oxygen atoms. As used herein, "silicone" and "siloxane" are used interchangeably.

As used herein, the term "silanol-functional silicone" and similar terms refer to silicones comprising silanol functional groups-SiOH.

As used herein, the term "substrate" refers to the surface of an article to be coated and may refer to a coating disposed on an article that is also considered a substrate.

As used herein, the term "target area" means a portion of the surface area of any substrate to be coated when a coating composition, such as a first, second, or third coating composition, is applied. The target area typically does not comprise the entire surface area of a given substrate. The term "non-target area" means the remainder of the substrate surface area and includes all areas outside of the substrate. In applying multiple coating compositions, the target area and the non-target area may be different for each application of one coating composition.

As used herein, the term "thermoset" means a polymer or resin having functional groups that react with a crosslinking agent or another polymer or functional group in a molecule to form a network material, thereby irreversibly converting a "soft" polymer into a more rigid form. In many cases, thermoset refers to a resin that "sets" irreversibly upon curing or crosslinking, wherein the polymer chains of the resin are linked together by covalent bonds. Once cured or crosslinked, the thermosetting resin will not melt and be insoluble in most organic solvents when heat is applied.

As used herein, the term "thermoplastic" refers to polymers and resins that are not linked by covalent bonds and thus can undergo liquid flow upon heating and are soluble in certain solvents.

As used herein, the term "tip speed" refers to the speed at which the applicator traverses the surface of the substrate.

As used herein, the term "total solids" or "solids content" refers to a solids content determined according to ASTM D2369 (2015).

As used herein, the term "use conditions" means all temperatures and pressures, including ambient pressure, such as 101.3kPa (1 atm), as well as temperatures at which any coating composition is used, stored or applied, and may include temperatures as low as-10 ℃ and as high as 140 ℃.

As used herein, the term "transfer efficiency" refers to the weight percent of the coating composition applied to a substrate as compared to the weight of the coating composition exiting the applicator according to ASTM D5286-20.

As used herein, "topcoat" refers to the uppermost coating layer applied over another coating layer (such as a base coat) to provide a protective and/or decorative layer.

As used herein, the terms "two-part", "2-K" and "2-pack" refer to coating compositions comprising a first part comprising a crosslinkable resin and a second part comprising a crosslinker, wherein the first and second parts are maintained separately prior to use. The crosslinkable resin and the crosslinking agent are capable of reacting when combined to form a thermosetting composition.

As used herein, the term "vehicle" is used in its broadest sense and includes all types of vehicles such as, but not limited to, cars, minivans, SUVs (sport utility vehicles), trucks, semi-trucks; tractor, bus, truck, golf cart, motorcycle, bicycle, tram, trailer, ATV (all-terrain vehicle); pick-up trucks; heavy mobile equipment such as bulldozers, mobile cranes, and excavators; an aircraft; a watercraft; a vessel; and other modes of transportation.

As used herein, unless otherwise indicated, the term "viscosity" refers to a value determined at 25 ℃ and ambient pressure and reflects the fluid's resistance to flow when subjected to shear stress and/or shear strain.

As used herein, the term "volatile" refers to materials that are readily vaporizable under ambient conditions.

As used herein, the phrase "wt.%" refers to weight percent.

The present disclosure describes coating compositions comprising an organic solvent. The coating composition has a shear-thinning rheology profile, particularly at high shear rates (1000 s, as a non-limiting example ^-1 ) The coating composition has a viscosity low enough to flow through the opening in the high efficiency applicator and be applied to a surface with or without low shear (as a non-limiting example, 0.1s ^-1 ) The coating composition, when applied to a vertical surface, exhibits minimal or no sagging.

The coating compositions described herein comprise non-volatile and volatile components. The amount of non-volatile components is generally reflected in the measurement of the total solids in the coating composition. The volatile component compensates for the difference between the original weight of the material and the weight after the total solids of the coating composition are determined (total solids as determined according to ASTM D2369 (2015)).

The amount of volatile components in the coating composition may be at least 5wt.%, such as at least 10wt.%, at least 15wt.%, at least 20wt.%, at least 25wt.%, at least 30wt.%, at least 35wt.% and at least 40wt.%, and may be at most 90wt.%, such as at most 85wt.%, at most 80wt.%, at most 75wt.% and at most 70wt.%, and may be 5wt.% to 90wt.%, such as 10wt.% to 90wt.%, 10wt.% to 85wt.%, 10wt.% to 80wt.%, 10wt.% to 75wt.%, 10wt.% to 70wt.%, 20wt.% to 90wt.%, 20wt.% to 85wt.%, 20wt.% to 80wt.%, 20wt.% to 70wt.%, 30wt.% to 90wt.%, 30wt.% to 80wt.%, 30wt.% to 70wt.%, 40wt.% to 90wt.%, 10wt.% to 40wt.%, to 40wt.%, and 40wt.% to 40wt.%, based on the weight of the coating composition. When the amount of volatile components is too high or too low, the coating composition may not have the desired rheological profile, the individual flows may not merge as desired and/or the coating composition may unacceptably sag on the vertical substrate. The amount of volatile component in the coating composition can be any of the values recited above or ranges between any of the values recited above (and including such values).

The amount of organic solvent in the volatile components in the coating composition may be at least 70wt.%, such as at least 72.5wt.% and at least 75wt.%, and may be at most 100wt.%, such as at most 95wt.%, at most 92.5wt.%, and at most 90wt.%, and 70wt.% to 100wt.%, such as 70wt.% to 95wt.%, 70wt.% to 90wt.%, 72.5wt.% to 100wt.%, 72.5wt.% to 95wt.%, 72.5wt.% to 90wt.%, 75wt.% to 100wt.%, 75wt.% to 95wt.%, based on the weight of the volatile components in the coating composition. When the amount of organic solvent in the volatile component is too high or too low, the coating composition may not have the desired rheological profile, the separate streams may not merge as desired and/or the coating composition may not dry or cure as desired. The amount of organic solvent in the volatile component of the coating composition can be any of the values described above or ranges between any of the values described above (and including such values).

The amount of organic solvent in the coating composition may be at least 5wt.%, such as at least 10wt.%, at least 15wt.%, at least 20wt.%, at least 25wt.%, at least 30wt.%, at least 35wt.% and at least 40wt.%, and may be at most 90wt.%, such as at most 85wt.%, at most 80wt.%, at most 75wt.% and at most 70wt.%, and from 5wt.% to 90wt.%, such as 5wt.% to 85wt.%, 5wt.% to 80wt.%, 5wt.% to 75wt.%, 5wt.% to 70wt.%, 10wt.% to 90wt.%, 10wt.% to 85wt.%, 10wt.% to 80wt.%, 10wt.% to 75wt.%, 10wt.% to 70wt.%, 20wt.% to 90wt.%, 20wt.% to 85wt.%, 20wt.% to 80wt.%, 20wt.% to 75wt.%, 20wt.% to 70wt.%, 30wt.% to 90wt.%, 30wt.% to 85wt.%, 30wt.% to 80wt.%, 30wt.% to 75wt.%, 30wt.% to 70wt.%, 40wt.% to 90wt.%, 40wt.% to 85wt.%, 40wt.% to 80wt.%, 40wt.% to 75wt.% and 40wt.% to 70wt.%. When the amount of organic solvent is too high or too low, the coating composition may not have the desired rheological profile, the individual streams may not merge as desired and/or the coating composition may unacceptably sag on a vertical substrate. The amount of organic solvent in the coating composition may be any of the values recited above or ranges between any of the values recited above (and including such values).

The coating compositions described herein may be solvent borne compositions. As a non-limiting example, the organic solvent may dissolve or disperse the film-forming material and optionally other ingredients of the coating composition, and may be selected to have sufficient volatility to evaporate from the coating composition during the curing and/or drying process. Non-limiting examples of suitable organic solvents include aliphatic hydrocarbons such as mineral spirits and high flash point VM & P naphthas; aromatic hydrocarbons such as benzene, toluene, xylenes, and solvent naphthas 100, 150, 200, etc.; alcohols such as ethanol, n-propanol, isopropanol, n-butanol, etc.; ketones such as acetone, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, and the like; esters such as ethyl acetate, n-butyl acetate, n-hexyl acetate, pentyl propionate, and the like; diols such as butanediol; glycol ethers such as methoxypropanol and ethylene glycol monomethyl ether, monoethyl ether, monobutyl ether, and monohexyl ether of ethylene glycol, and the like. Mixtures of various organic solvents may also be used.

The amount of total solids in the coating composition may be at least 10wt.%, such as at least 15wt.%, at least 20wt.%, at least 25wt.%, and at least 30wt.%, and may be at most 95wt.%, such as at most 90wt.%, at most 85wt.%, at most 80wt.%, at most 75wt.%, at most 70wt.%, and at most 60wt.%, and from 10wt.% to 95wt.%, such as 10wt.% to 90wt.%, 10wt.% to 80wt.%, 10wt.% to 75wt.%, 10wt.% to 70wt.%, 15wt.% to 95wt.%, 15wt.% to 90wt.%, 15wt.% to 80wt.%, 15wt.% to 75wt.%, 15wt.% to 70wt.%, 20wt.% to 100wt.%, 20wt.% to 90wt.%, 20wt.% to 80wt.%, 20wt.% to 75wt.%, 20wt.% to 70wt.%, 25wt.% to 95wt.%, 25wt.% to 90wt.%, 25wt.% to 80wt.%, 25wt.% to 75wt.%, 25wt.% to 70wt.%, 30wt.% to 100wt.%, 30wt.% to 90wt.%, 30wt.% to 80wt.%, 30wt.% to 75wt.% and 30wt.% to 70wt.%. When the amount of total solids is too high or too low, the coating composition may not have the desired rheological profile, individual flows may not merge as desired and/or the coating composition may unacceptably sag on a vertical substrate. The amount of total solids in the coating composition can be any of the values recited above or ranges between any of the values recited above (and including such values).

The coating composition may have a "low solids content". Thus, the amount of total solids in the coating composition may be at least 5wt.%, such as at least 8wt.% and at least 10wt.%, and may be at most 25wt.%, such as at most 20wt.%, at most 15wt.% and at most 12wt.%, and 5wt.% to 25wt.%, 5wt.% to 20wt.%, 5wt.% to 15wt.%, 5wt.% to 12wt.%, 8wt.% to 25wt.%, 8wt.% to 20wt.%, 8wt.% to 15wt.%, 8wt.% to 12wt.%, 10wt.% to 25wt.%, 10wt.% to 20wt.%, 10wt.% to 15wt.% and 10wt.% to 12wt.%, based on the weight of the coating composition. The amount of total solids in the low solids coating composition can be any of the values described above or a range between any of the values described above (and including the values).

As a non-limiting example, the coating composition may have a coating composition of at least 0.1s ^-1 (low shear rate) and a viscosity measured at 25 ℃, measured at 25 ℃ using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with DG26.7 measurement system, the viscosity may be at least 1,000cps, such as at least 2,000cps, at least 3,000cps and at least 4,000cps, and may be at most 30,000cps, such as at most 25,000cps, at most 20,000cps and at most 15,000cps, and may be 1,000cps to 30,000cps, such as 1,000cps to 25,000cps, 1,000cps to 20,000cps, 1,000cps to 15,000cps, 2,000cps to 30,000cps, 2,000cps to 20,000cps, 2,000cps to 15,000cps, 3,000cps to 30,000cps, 3,000 to 20,000cps, 3,000 to 15,000cps, 4,000cps to 30,000cps, 4,000cps to 4,000cps, and 4,000cps to 15,000cps. If at 0.1s ^-1 The viscosity of the coating composition measured is too high or too low, the coating composition may not flow properly through the applicator, individual flows may not merge as desired, and/or the coating composition may unacceptably sag on a vertical substrate. At 0.1s ^-1 The measured viscosity of the coating composition may be any of the above values or a range between any of the above values (and including the values).

As a non-limiting example, the coating composition may have a temperature of 25℃at 1000s ^-1 (high shear Rate, unless otherwise indicated, high shear Rate means 1000s ^-1 ) Viscosity measured below was measured using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with DG26.7 measurement system at 1000s ^-1 The viscosity may be at least 25cps, such as at least 35cps, at least 40cps, at least 45cps, at least 60cps, at least 63cps, and at least 68cps, and may be at most 150cps, such as at most 140cps, 130cps, and at most 125cps, and may be 25cps to 150cps, such as 25cps to 140cps, 25cps to 130cps, 25cps to 125cps, 35cps to 150cps, 35cps to 140cps, 35cps to 130cps, 35cps to 125cps, 40cps to 150cps, 40cps to 140cps, 40cps to 130cps, 40cps to 125cps, 60cps to 150cps, 60cps to 140cps, 60cps to 130cps, and 60cps to 125cps, measured below. If at 1000s ^-1 The viscosity of the coating composition measured is too highOr too low, the coating composition may not flow properly through the applicator, individual flows may not merge as desired, and/or the coating composition may unacceptably sag on a vertical substrate. At 1000s ^-1 The measured viscosity of the coating composition may be any of the above values or a range between any of the above values (and including the values).

The coating composition has a shear-thinning rheological profile, in other words, the viscosity of the coating composition at low shear rates is higher than the viscosity at high shear rates. As a non-limiting example, measured at 25 ℃ using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with DG26.7 measurement system, the coating composition may have a viscosity ratio, which may be at 1000s ^-1 At least 6 times, such as at least 10 times, at least 20 times, at least 30 times and at least 40 times, and may be at most 1,200 times, at most 1,000 times, at most 750 times, at most 500 times and at most 350 times the viscosity of the coating composition measured at (high shear rate) at 0.1s ^-1 (Low shear Rate, unless otherwise indicated, low shear Rate means 0.1s ^-1 ) Viscosity measured at 0.1s ^-1 The viscosity measured at this point may be 1000s ^-1 The viscosity of the coating composition measured below is 6 to 1,200 times, such as 6 to 1,000 times, 6 to 750 times, 6 to 500 times, 6 to 350 times, 10 to 1,200 times, 10 to 1,000 times, 10 to 750 times, 10 to 500 times, 10 to 350 times, 20 to 1,200 times, 20 to 1,000 times, 20 to 750 times, 20 to 500 times, 20 to 350 times, 30 to 1,200 times, 30 to 1,000 times, 30 to 750 times, 30 to 500 times, 30 to 350 times, 40 to 1,200 times, 40 to 1,000 times, 40 to 750 times, 40 to 500 times, and 40 to 350 times. If the shear-thinning properties of the coating composition are too high or too low, the coating composition may not flow properly through the applicator, the separate flows may not merge as desired and/or the coating composition may unacceptably sag on the vertical substrate. The shear thinning properties of the coating composition may be any of the values described above or ranges between any of the values described above (and including such values).

The viscosity of the coating composition can be measured by various techniques known in the art, non-limiting examples including parallel plate, cone plate, and cup spindle methods. As mentioned, the viscosity ratio can be observed independently of the method used. As a non-limiting example, the measurements of rheological properties described herein may be determined using Instruments available from Anton Paar (MCR 301, MCR 302, MCR 502, and MCR 702) and Instruments available from TA Instruments (ARES-G2, discovery HR 10, discovery HR 20, and Discovery HR 30).

As a specific non-limiting example, the viscosity of the coating composition may be measured using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with a DG26.7 measurement system, using 1000s ^-1 For 30s, and then using 0.1s ^-1 Is measured for 180 seconds.

As a specific non-limiting example, the viscosity of the coating composition can be measured using an Anton-Paar MCR 301 rheometer using a 50 mm parallel plate-plate clamp with temperature control. The plate-to-plate distance was kept a fixed distance of 0.2mm and the temperature was constant at 25 ℃.

Recovery time of the coating composition can be determined using an Anton Paar MCR 301 rheometer with a double gap cylinder as described above. Exposing the coating to 1000s ^-1 After 30s at high shear rate of (2) the recovery time was measured as a low shear test (shear rate of 0.1s ^-1 ) The time between the onset of the composition and the point at which the viscosity of the composition was 63% of the previous value before exposure to the high shear rate.

The recovery time of the coating composition may be at least 1 second, such as at least 1.5 seconds, at least 2 seconds, at least 3 seconds, and at least 5 seconds, and may be at most 100 seconds, such as at most 75 seconds, at most 50 seconds, at most 25 seconds, and at most 19 seconds, and may be 1 to 100 seconds, such as 1 to 75 seconds, 1 to 50 seconds, 1 to 25 seconds, 1 to 19 seconds, 1.5 to 100 seconds, 1.5 to 75 seconds, 1.5 to 50 seconds, 1.5 to 25 seconds, 1.5 to 19 seconds, 2 to 100 seconds, 2 to 75 seconds, 2 to 50 seconds, 2 to 25 seconds, 2 to 19 seconds, 3 to 100 seconds, such as 3 to 75 seconds, 3 to 50 seconds, 3 to 25 seconds, 3 to 19 seconds, 5 to 100 seconds, 5 to 75 seconds, 5 to 50 seconds, 5 to 25 seconds, and 5 to 19 seconds. When the recovery time is too short, the deposition of the coating composition may not be satisfactorily combined. When the recovery time is too long, the coating composition may exhibit undesirable sagging. The recovery time of the coating composition may be any of the above values or a range between any of the above values (and including the values).

The film-forming ingredients of the coating composition may include polymers, resins, crosslinkers, or any combination thereof capable of forming a film when applied to a substrate.

Polymers and resins included in the coating composition as film-forming ingredients include those commonly used in coating compositions. Non-limiting examples of suitable polymers and resins include acrylic resins, polyester resins, alkyd resins, polyurethane resins, polyolefin resins, silanes, epoxy resins, and silicone resins, and combinations thereof. The polymers and resins included as film-forming ingredients in the coating composition can have an amount of at least 250g/mol, such as at least 500g/mol, at least 750g/mol, and at least 1,000g/mol, and can be at most 500,000g/mol, such as at most 100,000g/mol, at most 50,000g/mol, at most 20,000g/mol, and at most 10,000g/mol, and can be 250 to 500,000g/mol, such as 500 to 500,000g/mol, 750 to 500,000g/mol, 250 to 100,000g/mol, 500 to 100,000g/mol, 750 to 100,000g/mol, 1,000 to 100,000g/mol, 250 to 50,00g/mol, 500 to 50,000g/mol, 1,000 to 50,000g/mol, 250 to 20,000g/mol, 750 to 20,000g/mol, 1,000 to 20,000g/mol, 250 to 10,000g/mol, 10,000 to 10,000. The weight average molecular weight of the polymers and resins included as film-forming ingredients in the coating composition may be at least 500g/mol, such as at least 800g/mol, at least 1,200g/mol, and at least 2,000g/mol, and may be up to 500,000g/mol, such as up to 200,000g/mol, and up to 50,000g/mol, and 500 to 500,000g/mol, such as 800 to 500,000g/mol, 1,200 to 500,000g/mol, 2,000 to 500,000g/mol, 500 to 200,000g/mol, 800 to 200,000g/mol, 1,200 to 200,000g/mol, 2,000 to 200,000g/mol, 500 to 50,000g/mol, 800 to 50,000g/mol, 1,200 to 50,000g/mol, and 2,000 to 50,000g/mol. The number average molecular weight and the weight average molecular weight of the polymer and the resin included in the coating composition as film-forming ingredients may be any of the values described above or ranges between any of the values described above (and include the values).

In many cases, the polymers and resins may have crosslinkable functional groups. Non-limiting examples of suitable crosslinkable functional groups include urethanes, carboxylic acids, alkoxysilanes, hydroxyl groups, carboxyl groups, epoxy groups, ultraviolet curable functional groups, and combinations thereof. In the coating composition, the polymer and the resin may be used singly or two or more may be used in combination.

One suitable class of film-forming polymers for the film-forming resin includes, but is not limited to, those derived from ethylenically unsaturated monomers. Particularly useful members of this class are acrylic polymers, such as polymers of alkyl esters of (meth) acrylic acid or copolymers optionally together with other ethylenically unsaturated monomers. These polymers may be thermoset and crosslinkable. Suitable (meth) acrylates include, but are not limited to, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate. Cyclic esters such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and hydroxyalkyl esters such as 2-hydroxy (meth) ethyl acrylate, 2-hydroxypropyl (meth) acrylate may also be used. In addition, vinyl aliphatic or vinyl aromatic compounds such as (meth) acrylonitrile, styrene, vinyl acetate, vinyl propionate and vinyl toluene may be used. For crosslinking, suitable functional monomers used in addition to the above monomers include (meth) acrylic acid, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N- (alkoxymethyl) and (meth) acrylamides, wherein the alkoxy groups can be, as non-limiting examples, butoxy groups, glycidyl acrylate and/or glycidyl methacrylate.

As a non-limiting example, the film-forming resin may include a polyester polyol, which may be prepared in a known manner by condensation of a polyol and a polycarboxylic acid. Suitable polyols include ethylene glycol, propylene glycol, butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane and pentaerythritol. Suitable polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid. In addition to the polycarboxylic acids mentioned above, functional equivalents of the acids in the presence of them (such as anhydrides) or lower alkyl esters of the acids (such as methyl esters) can also be used.

As a non-limiting example, the film-forming resin can include an acrylic polyol, which can be prepared from a monomer mixture comprising a hydroxy-functional monomer. Mixtures of different acrylic polyols may be used. The hydroxy-functional monomer may include a hydroxyalkyl group. Suitable acrylic polyols include copolymers of alkyl esters of (meth) acrylic acid optionally together with other polymerizable ethylenically unsaturated monomers.

Non-limiting examples of hydroxy-functional monomers that may be used in the acrylic polyol include hydroxyalkyl (meth) acrylates, typically having 2 to 12 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate, and the like; (meth) acrylic acid (4- (hydroxymethyl) cyclohexyl) methyl ester; hydroxy-functional adducts of caprolactone and hydroxyalkyl (meth) acrylate, and beta-hydroxy ester functional monomers, reaction products of glycidyl methacrylate with versatic acid, and Cardura ^TM Reaction products of E10p glycidyl esters (obtainable from Hexion) with methacrylic acid. The hydroxy-functional monomer may be at least 5wt.%, such as at least 10wt.% and at least 15wt.%, and may be at most 70wt.%, at most 60wt.%, at most 50wt.%, at most 45wt.% and at most 40wt.%, and may be 5 to 70wt.%, such as 10 to 70wt.%, 15 to 70wt.%, 5 to 60wt.%, 10 to 60wt.%, 15 to 60wt.%, 5 to 50wt.%Amounts of wt.%, 10 to 50wt.%, 15 to 50wt.%, 5 to 40wt.%, 10 to 40wt.%, and 15 to 40wt.% are contained in the monomer mixture based on the total weight of monomers in the monomer mixture used to prepare the acrylic polyol. The amount of hydroxy-functional monomer used in the acrylic polyol may be any of the values or ranges between any of the values (and including the values).

The acrylic polyol may have at least 1,000g/mol, such as at least 2,000g/mol, at least 3,000g/mol, at least 5,000g/mol, and at least 5,500g/mol, and may be at most 50,000g/mol, such as at most 30,000g/mol, at most 15,000g/mol, at most 10,000g/mol, and at most 7,500g/mol, and may be 1,000 to 50,000g/mol, such as 1,000 to 30,000g/mol, 1,000 to 15,000g/mol, 1,000 to 10,000g/mol, 1,000 to 7,500g/mol, 2,000 to 50,000g/mol, 2,000 to 10,000g/mol, 2,000 to 7,500g/mol, 3,000 to 30,000g/mol, 3,000 to 15,000g/mol, 000 to 10,000g/mol, 3,000 to 7,500,000 g/mol, 5,000 to 5,000g/mol, and a weight average of the acrylic polyol. The weight average molecular weight reported herein can be determined by Gel Permeation Chromatography (GPC) using suitable polystyrene standards. The weight average molecular weight of the acrylic polyol may be any of the values or a range between any of the values (and including the values).

Useful alkyl esters of (meth) acrylic acid include, but are not limited to, aliphatic alkyl esters containing from 1 to 30 carbon atoms in the alkyl group, and typically from 2 to 18 carbon atoms. Non-limiting examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Suitable other copolymerizable ethylenically unsaturated monomers include vinylaromatic compounds such as styrene and vinyl toluene; nitriles such as (meth) acrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride, and vinyl esters such as vinyl acetate.

Film-forming resins may include polyesters and polyesters functionalized with urethanes.

Non-limiting examples of suitable crosslinking agents include: diisocyanates, dihydrazides, diepoxides, and condensates of formaldehyde with nitrogen-containing compounds such as urea, thiourea, melamine or benzoguanamine, or lower alkyl ethers of such condensates, wherein the alkyl groups usually contain from 1 to 4 carbon atoms, are commonly referred to as aminoplasts. Other non-limiting examples of crosslinking agents are melamine-formaldehyde condensates in which a majority of the methylol groups have been etherified by reaction with butanol or an alcohol such as ethanol or methanol, carbodiimides, polyols, phenolic resins, epoxy resins, beta-hydroxy (alkyl) amide resins, hydroxy (alkyl) urea resins, oxazolines, alkylated urethane resins, (meth) acrylates, isocyanates, blocked isocyanates, polyacids, anhydrides, organometallic acid functional materials, polyamines, polyamides, aziridines, and combinations thereof.

Any of these crosslinking agents known to those skilled in the art for use with curable acrylic polymers may be used. For the foregoing purposes, the crosslinker (when present) may be considered as part of the film-forming resin material.

Other non-limiting examples of suitable polymer classes that can be used as curable film-forming resins are:

(i) Polyepoxides and polyacid crosslinking agents;

(ii) (meth) acryl silane polymer, (meth) acrylic polyol polymer, alkylated melamine-formaldehyde crosslinking agent; and

(iii) Polyisocyanates and polymers having groups reactive with isocyanates.

Non-limiting examples of polyisocyanates include aliphatic and aromatic polyisocyanates and mixtures thereof. As specific non-limiting examples, higher polyisocyanates, such as isocyanurates of diisocyanates, may be used; diisocyanates, uretdiones and biurets may also be used. Isocyanate prepolymers may also be used, non-limiting examples of which include the reaction products of polyisocyanates with polyols. Mixtures of polyisocyanate crosslinkers can be used.

As non-limiting examples, the polyisocyanate may be prepared from a variety of isocyanate-containing materials. Non-limiting examples of suitable polyisocyanates include trimers prepared from the following diisocyanates: toluene diisocyanate, 4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, an isomeric mixture of 2, 4-trimethylhexamethylene diisocyanate and 2, 4-trimethylhexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, tetramethylxylylene diisocyanate and/or 4,4' -benzhydryl diisocyanate. In addition, blocked polyisocyanate prepolymers of various polyols (such as polyester polyols) may also be used.

The isocyanate groups may be blocked or unblocked as desired. If the polyisocyanate is to be blocked or capped, any suitable aliphatic, cycloaliphatic or aromatic alkyl monol or phenol compound known to those skilled in the art may be used as the capping agent for the polyisocyanate. Non-limiting examples of suitable blocking agents include those materials that will deblock at high temperatures, such as aliphatic alcohols, including methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic alkyl alcohols such as benzyl alcohol and methyl phenyl methanol; and phenolic compounds such as phenol itself and substituted phenols, wherein the substituents do not interfere with the coating operation, such as cresols and nitrophenols. Glycol ethers may also be used as capping agents. Non-limiting examples of suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. Non-limiting examples of other suitable blocking agents include oximes such as methyl ethyl ketone oxime, acetone oxime, and cyclohexanone oxime, lactams such as epsilon-caprolactam, pyrazoles such as dimethylpyrazole, and amines such as dibutylamine.

The coating composition may be formulated as a single-pack (1K), double-pack (2K) or multi-pack coating composition, depending on whether a crosslinker is used or not and the composition of the coating composition. As non-limiting examples, the one-pack coating composition may be an air-dried coating or an unactivated coating that dries primarily by solvent evaporation and does not require crosslinking to form a coating film having the desired properties. As a non-limiting example, a single package may contain a combination of a reactive functional polymer and a crosslinker that is stable during storage and that reacts only when subjected to high temperatures. As a non-limiting example, if a polyisocyanate having free isocyanate groups is used as the crosslinker, the coating composition may be formulated as a two-pack or multi-pack coating composition, as the crosslinker may be mixed with the other components of the coating composition just prior to coating application. As a non-limiting example, if, for example, blocked polyisocyanates are used as crosslinkers, the coating composition may be formulated as a one-pack (1K) coating composition. As a non-limiting example, a single package (1K) formulation may react with atmospheric moisture and crosslink.

The amount of film-forming resin in the coating composition generally comprises any film-forming polymer and crosslinker contained in the coating composition. The amount of film-forming resin in the coating composition may be at least 0.1wt.%, such as at least 0.5wt.%, at least 1wt.%, at least 5wt.%, at least 10wt.%, at least 15wt.% and at least 20wt.%, and may be at most 70wt.%, such as at most 65wt.%, at most 60wt.%, at most 55wt.% and at most 50wt.%, and may be 0.1wt.% to 70wt.%, such as 0.5wt.% to 70wt.%, 1wt.% to 70wt.%, 5wt.% to 70wt.%, 10wt.% to 70wt.%, 15wt.% to 70wt.%, 20wt.% to 70wt.%, 1wt.% to 60wt.%, 5wt.% to 60wt.%, 10wt.% to 60wt.%, 15wt.% to 60wt.%, 20wt.% to 60wt.%, 1wt.% to 50wt.%, 5wt.% to 50wt.%, 10wt.% to 50wt.%, 15wt.% to 50wt.% and 20wt.% to 50wt.%, based on the weight of the coating composition. If the amount of film-forming resin is too low, the final coating may not have the desired properties, and if the amount of film-forming resin is too high, the coating composition may not have the desired rheological profile. The amount of film-forming resin in the coating composition can be any of the values recited above or ranges between any of the values recited above (and including such values). The number average and weight average molecular weights of the film-forming resins are as described above.

The coating compositions described herein may be thermosetting compositions.

When using a 1-K composition as described herein, the coating composition may comprise an alkoxy and/or silanol functional silicone. Non-limiting examples of suitable silanol-functional silicones that can be used in the coating compositions described herein are disclosed in U.S. patent No. 8,722,835, column 3, line 27 to column 4, line 3, the specific disclosure of which is incorporated herein by reference. The coating composition may comprise an alkoxy-functional silicone. Non-limiting examples of suitable alkoxy-functional silicones that can be used in the coating compositions described herein are disclosed in U.S. patent No. 8,722,835, column 4, line 32 to column 5, line 6, the specific disclosure of which is incorporated herein by reference. The alkoxy and/or silanol functional silicone may have a weight average molecular weight of at least 200g/mol, such as at least 700g/mol and at least 1,000g/mol, and may be at most 300,000g/mol, such as at most 200,000g/mol and at most 100,000 g/mol. The weight average molecular weight of the alkoxy-and/or silanol-functional silicone can be any or between (and including) the values recited above. The weight average molecular weight can be determined by Gel Permeation Chromatography (GPC) using suitable polystyrene standards.

When multi-pack or 2-K compositions are used as described herein, the coating composition may comprise an epoxy-polysiloxane composition. Non-limiting examples of suitable epoxy-polysiloxane compositions that can be used in the coating compositions described herein are disclosed in U.S. patent No. 8,722,835, column 15, line 4 to line 45, the specific disclosure of which is incorporated herein by reference.

The coating composition may be a clear coat. When used as a clear coat, the coating composition provides a top coat that is optionally used with a multilayer coating system. The coating composition may be free of colorants. Furthermore, the transparent coating may be an at least substantially transparent or completely transparent coating. The transparent coating may contain colorants that do not interfere with the desired transparency of the transparent top coating.

The coating composition may comprise pigments and/or dyes as colorants. Non-limiting examples of suitable pigments include organic and/or inorganic materials, untreated aluminum, treated aluminum (containing silica, inorganic pigments, and/or organic pigments), titanium dioxide, zinc oxide, iron oxide, carbon black, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt (lakes), benzimidazolone, condensation, metal complexes, isoindolinone, isoindoline, and polycyclic phthalocyanines, quinacridone, perylene, peryleneone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, huang Entong, pyranthrone, anthrone, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole red ("DPPBO red"), monoazo red, iron oxide red, quinacridone chestnut, transparent red oxide, cobalt blue, iron oxide yellow, chromium titanate yellow, nickel titanate yellow, transparent yellow oxide yellow, chromic acid yellow, bismuth vanadate yellow, pre-chrome yellow, transparent red oxide red flake, iron oxide red, molybdenum oxide red, radar red, orange, light-reflective pigments, orange, and combinations thereof.

Non-limiting examples of suitable dyes include those based on solvents and/or water such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, non-limiting examples include bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigo, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene and triphenylmethane, dioxazine carbazole violet, phthalocyanine blue, indanthrone blue, monoazo permanent orange, ferrite yellow, benzidine yellow, indole dione yellow, monoazo yellow, benzimidazolone yellow, isoindoline yellow, tetrachloroisoindoline yellow, bisazo yellow, cognthraquinone orange, quinacridone orange, benzimidazolone orange, phthalocyanine green, quinacridone red, azo red, diketopyrrolopyrrole red, perylene scarlet or perylene chestnut, quinacridone violet, thioindigo red, and combinations thereof.

The coating composition may comprise radar-reflective pigments or LiDAR-reflective pigments or infrared-reflective pigments. LiDAR, radar-reflective pigments, or infrared-reflective pigments may include, but are not limited to, nickel manganese ferrite black (pigment black 30), chrome brown black (CI pigment green 17, CI pigment brown 29, and 35), pigment blue 28, pigment blue 36, pigment green 26, pigment green 50, pigment brown 33, pigment brown 24, pigment black 12, and pigment yellow 53, and combinations thereof.

As a non-limiting example, the LiDAR reflective pigment may include a semiconductor and/or dielectric ("SCD") in which a metal may be dispersed. The medium (e.g., SCD) in which the metal may be dispersed may also be referred to herein as a matrix. The metal and the matrix may form a heterogeneous mixture that may be used to form the pigment. The metal may be dispersed uniformly or non-uniformly throughout the matrix. As non-limiting examples, the semiconductor of the LiDAR reflective pigment may include silicon, germanium, silicon carbide, boron nitride, aluminum nitride, gallium nitride, silicon nitride, gallium arsenide, indium phosphide, indium nitride, indium arsenide, indium antimonide, zinc oxide, zinc sulfide, zinc telluride, tin sulfide, bismuth sulfide, nickel oxide, boron phosphide, titanium dioxide, barium titanate, iron oxide, doped forms thereof (i.e., dopants such as boron, aluminum, gallium, indium, phosphorus, arsenic, antimony, germanium, nitrogen), alloyed forms thereof, other semiconductors, or combinations thereof are added at a weight percentage of 0.01% or less based on the weight of the LiDAR reflective pigment. As a non-limiting example, the LiDAR reflective pigment may comprise silicon. The dielectric of the LiDAR reflective pigment may include a solid insulating material (e.g., silica), a ceramic (e.g., alumina, yttria Alumina Garnet (YAG), neodymium doped YAG (Nd: YAG)), a glass (e.g., borosilicate glass, soda lime silicate glass, phosphate glass), an organic material, doped forms thereof, other dielectrics, or combinations thereof. The organic material may include, for example, acrylic, alkyd, chlorinated polyether, diallyl phthalate, epoxy-polyamide, phenolic, polyamide, polyimide, polyester (e.g., PET), polyethylene, polymethyl methacrylate, polystyrene, polyurethane, polyvinyl butyral, polyvinyl chloride (PVC), copolymers of PVC and vinyl, radical acetate, polyvinyl formal, polyvinylidene fluoride, xylene, silicone, copolymers of nylon and nylon, polyamide-polyimide, polyolefin, polytetrafluoroethylene, other polymers, or combinations thereof. If the dielectric comprises an organic material, the organic material is selected such that the pigment formed therefrom resists melting and/or changes in dimensional or physical characteristics when incorporated into a coating, film and/or article formulation. The metal in the LiDAR reflective pigment may include, for example, aluminum, silver, copper, indium, tin, nickel, titanium, gold, iron, alloys thereof, or combinations thereof. The metal may be in particulate form and may have an average particle size in the range of 0.5nm to 100nm, such as 1nm to 10nm, as measured by Transmission Electron Microscopy (TEM) at 100 kV. The metal may be in particulate form and may have an average particle size of less than or equal to 20nm as measured by TEM. Suitable methods for measuring particle size by TEM include suspending metal particles in a solvent and then casting the suspension droplets onto a TEM grid, which is allowed to dry at ambient conditions. Particle size measurements can be obtained from images acquired using a Tecnai T20 TEM operating at 200kV and analyzed using ImageJ software or equivalent instruments and software.

As a non-limiting example, the coating composition may include a corrosion inhibiting pigment. Any suitable corrosion inhibiting pigment known in the art may be used in the coating composition, non-limiting examples including calcium strontium zinc phosphosilicate; di-orthophosphate, wherein one of the cations is represented by zinc, non-limiting examples are Zn-Al, zn-Ca, zn-K, zn-Fe, zn-Ca-Sr, ba-Ca, sr-Ca and combinations thereof; a combination of phosphate anions and preservative effective anions, non-limiting examples of preservative effective anions being silicate ions, molybdate ions, and borate ions; modified phosphate pigments modified by organic corrosion inhibitors and combinations thereof. Non-limiting examples of modified phosphate pigments include aluminum (III) zinc (II) phosphate, basic zinc phosphate, molybdenum zinc calcium phosphate, boron zinc phosphate, zinc strontium phosphosilicate, calcium barium phosphosilicate, calcium strontium zinc phosphosilicate, and combinations thereof. Other non-limiting examples of corrosion inhibiting pigments that may be used in the coating formulation include zinc 5-nitroisophthalic acid, calcium cyanurate, metal salts of dinonylnaphthalene sulfonic acid, and combinations thereof.

When a colorant is included in the coating composition, the colorant may be included at a level of at least 0.1wt.%, such as at least 0.15wt.%, at least 0.2wt.%, at least 0.5wt.%, and at least 1wt.% and may be included at a level of up to 40wt.%, such as up to 37wt.% and up to 34wt.%, based on the weight of the coating composition. Further, the amount of colorant may be from 0.1 to 40wt.%, such as from 0.15 to 38wt.% and from 1 to 34, based on the weight of the coating composition. When the amount of the colorant is too low, a desired color effect from the paint may not be achieved. When the amount of colorant is too high, the rheological profile of the coating composition may be adversely affected. When a colorant is included in the coating composition, the colorant may be included at any of the levels described above or in a range between any of the levels described above (and including such levels).

As non-limiting examples, the coating composition may include various other components such as binders, carriers, water, catalysts, conventional additives, or combinations thereof. Conventional additives may include, but are not limited to, dispersants, antioxidants and absorbents, wetting agents, leveling agents, defoamers, anti-cratering agents, thermoplastic resins, plasticizers, abrasion resistant particles, fillers (including, but not limited to, mica, talc, clays, and inorganic minerals), metal oxides, metal flakes, various forms of carbon, antioxidants, hindered amine light stabilizers, ultraviolet light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, reactive diluents, catalysts, reaction inhibitors, corrosion inhibitors, other conventional adjuvants, and combinations thereof. The coating composition may be suitable for application to a substrate.

As a non-limiting example, when a metallic flake pigment is used, it can have an aspect ratio of 5:1 to 500:1, such as 10:1 to 200:1.

As noted above, the coating compositions have a shear-thinning rheological profile, typically non-newtonian behavior, in which the viscosity decreases at increased shear strain. Thus, a shear-thinning rheology profile may be achieved by including a rheology modifier in the coating composition. Rheology modifiers may include natural gums, synthetic resins, organoclays, hydrogenated castor oils, fumed silica, polyamides, overbased sulfonates, inorganic crystals, nonaqueous dispersions, organoclays and polyurea compounds that are sparingly soluble in organic solvents.

Rheology modifiers may be included in the coating composition to provide a variety of rheological properties. As a non-limiting example, the rheology modifier may provide a desired high shear viscosity that allows the coating composition to flow through the applicator and a low shear viscosity that is high enough to minimize sagging on a vertical substrate but not so high as to prevent the applied flows from merging on the substrate to form a uniform coating. As another non-limiting example, the rheology modifier may provide a desired recovery time that is short enough to minimize sagging on a vertical substrate, but not so short as to prevent the applied streams or droplets from merging on the substrate to form a uniform coating.

The rheology modifier may be present in the coating composition at a level of at least 0.1wt.%, such as at least 0.2wt.%, at least 0.5wt.%, at least 0.6wt.% at least 0.75wt.% and more than 1wt.%, and may be present in the coating composition at a level of at most 25wt.%, such as at most 15wt.%, at most 12.5wt.% and at most 10wt.%, and is 0.1wt.% to 25wt.%, such as 0.2wt.% to 25wt.%, 0.5wt.% to 25wt.%, 0.75wt.% to 25wt.%, 1wt.% to 25wt.%, 0.1wt.% to 15wt.%, 0.2wt.% to 15wt.%, 0.5wt.% to 15wt.%, 1wt.% to 15wt.%, 0.1wt.% to 10wt.%, 0.2wt.% to 10wt.%, 0.5wt.% to 10wt.%, 0.75wt.% to 10wt.% and 1wt.% to 10wt.%, based on the weight of the coating composition. If the amount of rheology modifier is less than or greater than the amount described above, the coating composition may not have the desired rheology profile described herein. The amount of rheology modifier included in the coating composition may be any of the values described above or ranges between any of the values described above (and including such values).

One class of rheology modifiers includes Sag Control Agents (SCAs). Non-limiting examples of SCAs include polyureas, polyamides, polyamide waxes, crosslinked polymer particles, inorganic layered silicates, magnesium aluminum silicate, sodium magnesium silicate layered, sodium magnesium lithium silicate layered, montmorillonite, kaolin, silica, polyvinyl alcohol, poly (meth) acrylamides, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride copolymers, and ethylene-maleic anhydride copolymers. The amount of the flow control agent in the coating composition may be at least 0.1wt.%, such as at least 0.25wt.% and at least 0.5wt.%, and may be at most 6wt.%, such as at most 5wt.%, 4wt.% and at most 3wt.%, and 0.1wt.% to 6wt.%, such as 0.25wt.% to 6wt.%, 0.5wt.% to 6wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.% and 0.5wt.% to 3wt.%. When the amount of SCA is too low, the coating composition may exhibit undesirable sagging. When the amount of SCA is too high, the coating composition may not exhibit the desired rheological profile as described herein. The amount of SCA included in the coating composition can be any of the above values or ranges between any of the above values (and including the values). The SCA may have a number average molecular weight of 380g/mol to 1,000 g/mol.

As non-limiting examples, the rheology modifier may include a combination of insoluble spheres, low density non-porous particles, and insoluble needle or rod crystals to provide a combination of desired rheological properties.

Non-limiting examples of insoluble spheres include submicron-sized particles produced via non-aqueous dispersion polymerization. In addition to contributing to the rheological profile of the coating composition, submicron sized particles can also prevent crack propagation, improve toughness, and reduce the energy requirements of drying the coating composition. Non-limiting examples include super crosslinked polymeric microspheres, highly crosslinked acrylic polymer particles, and crosslinked hydroxy functional polyacrylic resins, alone or in any combination, many of which are available under the SETALUX brand from ALLNEX Netherlands b.v.

Non-limiting examples of suitable non-aqueous dispersions include internally crosslinked organic polymers. The internally crosslinked organic polymer may be in a non-aqueous dispersion and may include an acrylic polymer and may be prepared from a monomer mixture comprising monomers having functional groups that allow crosslinking with itself and possibly with adjacent polymers, allowing the formation of gels or microgels. As a non-limiting example, any monomer known in the art containing at least two ethylenically unsaturated double bonds may be included in the monomer mixture. Suitable monomers include, but are not limited to, di (meth) acrylates (e.g., hexanediol di (meth) acrylate), ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, decanediol di (meth) acrylate, or combinations of di (meth) acrylates. Non-limiting examples of suitable internal cross-linked organic polymers can be prepared from monomer mixtures comprising: (i) methyl methacrylate; (ii) butyl acrylate; (iii) styrene; and (iv) ethylene glycol dimethacrylate. Non-limiting examples for preparing the non-aqueous dispersion can be found in column 4, line 61 to column 6, line 60 of U.S. patent No. 4,147,688, and column 2, line 43 to column 6, line 13 of U.S. patent No. 9,434,828, the specific parts of which are incorporated herein by reference.

As a non-limiting example, the internally crosslinked organic polymer may be dispersed in an organic continuous phase comprising an organic solvent or polymer using high stress mixing or homogenization to form a non-aqueous dispersion. Non-limiting examples of nonaqueous media for use as the organic continuous phase include ketones, such as methyl amyl ketone, and glycol ethers, such as 2-butoxyethanol.

The particle size of the nonaqueous dispersion may be 0.1 to 1.2. Mu.m (Dv ₅₀ ) As measured by monochromatic light scattering using a spectrophotometer. Particle size can be measured by dynamic light scattering such as using Malvern Zetasizer, malvern Zetasizer is a high performance dual angle particle size analyzer for enhanced detection of aggregates and measurements made on small or diluted samples and very low or high concentration samples using dynamic light scattering. As used herein, "Dv ₅₀ "means the maximum particle diameter below which the sample volume is 50% of the median particle size by volume.

The amount of insoluble spheres in the coating composition may be at least 0.1wt.%, such as at least 0.25wt.% and at least 0.5wt.%, and may be at most 5wt.%, such as at most 4wt.% and at most 3wt.%, and 0.1wt.% to 5wt.%, such as 0.25wt.% to 5wt.%, 0.5wt.% to 5wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.%, 0.5wt.% to 3wt.%, based on the weight of the coating composition. When the amount of insoluble spheres is too low or too high, the coating composition may not exhibit the desired rheological profile as described herein. The amount of insoluble spheres included in the coating composition may be any value or range between any of the values recited above (and including such values).

Non-limiting examples of low density non-porous particles include fumed silica, and clays such as montmorillonite, bentonite, and kaolin, and combinations thereof.

As a non-limiting example, the low density non-porous particles may include silica-based rheology control agents, as a non-limiting example, fumed silica particles conventionally used as rheology control agents.

The amount of low density non-porous particles in the coating composition may be at least 0.1wt.%, such as at least 0.25wt.% and at least 0.5wt.%, and may be at most 5wt.%, such as at most 4wt.% and at most 3wt.%, and 0.1wt.% to 5wt.%, such as 0.25wt.% to 5wt.%, 0.5wt.% to 5wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.%, 0.5wt.% to 3wt.%, based on the weight of the coating composition. When the amount of low density non-porous particles is too low or too high, the coating composition may not exhibit the desired rheological profile as described herein. The amount of low density non-porous particles included in the coating composition can be any of the values described above or ranges between any of the values described above (and including such values).

Non-limiting examples of insoluble needle or rod shaped crystals include natural gums, calcites, organic transition metal complexes, reaction products of amines or polyamines with polyisocyanates, reaction products of aromatic amines with polyisocyanates, and combinations thereof. The isocyanate-containing material present as insoluble needle-like or rod-like crystals is separated from any isocyanate-containing material used as a crosslinker. Non-limiting examples of insoluble needle or rod shaped crystals may include the reaction product of benzylamine and hexane diisocyanate.

Without being limited to any single theory, insoluble needle or rod crystals may exhibit random orientation when not subjected to a shear stress and orient in a parallel fashion in a shear strain or flow direction when a shear stress is applied, such as when flowing through an applicator and one or more nozzles. The initial random orientation may be enhanced by polar moieties in the molecules that make up the needle-like or rod-like crystals that tend to associate with each other in the non-aqueous environment of the coating composition. As a non-limiting example, polar moiety association may include hydrogen bond formation between needle-type or rod-type crystals. It is believed that the initial random orientation and any polarity and/or hydrogen bonding enhancement will result in increased resistance to flow or upon application of sufficient shear stress to the coating composition, the induced flow and any association between crystals is disrupted, resulting in a substantial reduction in viscosity of the coating composition. Once the shear stress is removed, such as after application of the coating composition to a substrate, the insoluble needle-like or rod-like crystals transform into their random configuration and reform into any polar or hydrogen bond associations. In the latter state, the resistance to flow is restored and, as a non-limiting example, sagging of the coating composition on a vertical substrate is minimized.

Primary particle size (Dv) of insoluble needle-like or rod-like crystals ₅₀ ) May be in the micrometer or sub-micrometer range, and may be in the range of at least 0.1 μm, such as at least 0.5 μm and at least 1 μm, and may be at most 15 μm, such as at most 10 μm, at most 7.5 μm and at most 5 μm, and may be 0.1 μm to 15 μm, such as 0.1 μm to 10 μm, 0.1 μm to 7.5 μm, 0.1 μm to 5 μm, 0.5 μm to 15 μm, 0.5 μm to 10 μm, 0.5 μm to 7.5 μm, 0.5 μm to 5 μm, 1 μm to 15 μm, 1 μm to 10 μm, 1 μm to 7.5 μm and 1 μm to 5 μm (micrometers), as measured using a Malvern Zetasizer dynamic light scattering instrument. The primary particle size of the insoluble needle-like or rod-like crystals may be any of the above values or a range between any of the above values (and including the values).

Particle size may be measured using an instrument such as Mastersizer 2000 (available from Malvern, worcestershire, malvern Instruments of UK, ltd.). Mastersizer 2000 directs a laser beam (diameter 0.633mm, wavelength 633 nm) through the particle dispersion (to a shade of 2-3% in distilled, deionized or filtered water) and measures the dispersion's light scattering (measurement parameters: 25 ℃,2200rpm,30sec pre-measured delay, 10sec background measurement, 10sec sample measurement). The amount of light scattered by the dispersion is inversely proportional to the particle size. A series of detectors measure scattered light and the data is then analyzed by computer software (Malvern Mastersizer software, version 5.60) to generate a particle size distribution from which particle size can be conventionally determined. A sample of the particle dispersion may optionally be sonicated prior to analysis of particle size. The ultrasonic treatment process comprises the following steps: (1) Mixing the particle dispersion using a vortex mixer (Fisher Scientific Vortex Genie 2, or equivalent); (2) 15mL distilled deionized ultrafiltration water was added to a 20mL screw cap scintillation vial; (3) adding 4 drops of the dispersion to the vial; (4) mixing the contents of the vial using a vortex mixer; (5) The vial was capped and placed in an ultrasonic water bath (Fisher Scientific Model FS, or equivalent) for 5 minutes; (6) again vortex the vial; and (7) drop wise adding the sample to a Mastersizer to achieve a shade of between 2 and 3 for particle size distribution analysis as described above.

As a non-limiting example, insoluble needle or rod crystals can include urea-based compounds, which can include the reaction product of reactants including, as a non-limiting example, amines and isocyanates (in many cases in the form of bisureas). The reaction product may be crystalline. Non-limiting examples of suitable isocyanates include polyisocyanates. The polyisocyanate may be aliphatic, aromatic, or mixtures thereof. Higher polyisocyanates such as isocyanurates of diisocyanates may be used.

As non-limiting examples, the polyisocyanates used to prepare the insoluble needle-like or rod-like crystals can be prepared from a variety of isocyanate-containing materials. Non-limiting examples of suitable polyisocyanates include toluene diisocyanate, 4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, isomeric mixtures of 2, 4-trimethylhexamethylene diisocyanate and 2, 4-trimethylhexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, tetramethylxylylene diisocyanate and 4,4' -xylylene diisocyanate. Trimers prepared from these diisocyanates may also be used.

Suitable amines which can be used to prepare insoluble needle-like or rod-like crystals can be primary or secondary monoamines or mixtures thereof. The amine may be aromatic or aliphatic (e.g., cycloaliphatic). Non-limiting examples of suitable monoamines may include aliphatic polyamines such as ethylamine, isopropylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and benzylamine.

The amount of insoluble needle-or rod-like crystals in the coating composition may be at least 0.1wt.%, such as at least 0.25wt.% and at least 0.5wt.%, and may be at most 5wt.%, such as at most 4wt.% and at most 3wt.%,0.1wt.% to 5wt.%, such as 0.25wt.% to 5wt.%, 0.5wt.% to 5wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.%, 0.5wt.% to 3wt.%, based on the weight of the coating composition. When the amount of insoluble needle-like or rod-like crystals is too low or too high, the coating composition may not exhibit the desired rheological profile as described herein. The amount of insoluble needle-like or rod-like crystals included in the coating composition may be any of the values recited above or ranges between any of the values recited above (and including such values).

The present disclosure also relates to a method of forming a coating on at least a portion of a substrate. The method includes, but is not limited to, allowing any of the coating compositions described herein to flow through one or more applicators comprising one or more nozzles capable of imparting a shear stress on the coating composition. When the coating composition is exposed to high shear stress in the nozzle, its viscosity decreases as described above as it flows through the nozzle. As the coating composition exits the nozzle, it may form a continuous stream or discrete droplets. When the coating composition contacts the substrate, it forms a uniform coating.

The coating composition may be applied to a substrate that is placed substantially horizontally with respect to the ground. As used herein, a substrate that is "substantially horizontally" placed relative to the ground refers to a substrate that has at least a portion of the surface being coated parallel to the ground or parallel to the ground within 10 °, such as within 5 °.

The coating composition may be applied to a substrate that is placed substantially vertically relative to the ground. As used herein, a substrate that is placed "substantially perpendicular" to the ground refers to a substrate that has at least a portion of the surface being coated that is perpendicular to the ground or perpendicular to the ground within 45 °, such as within 40 °, within 30 °, within 20 °, within 10 °, or within 5 °.

The coating composition may have a surface tension such that the difference between the surface energy of the substrate and the surface tension of the coating composition either uncoated or having a coating applied thereto (surface energy of the substrate-surface tension of the coating composition) may be greater than 0, such as greater than 0.5mN/m, greater than 0.7mN/m, greater than 1mN/m and greater than 2mN/m, as measured according to DIN EN 14370:2004-1 1 (determination of surfactant-surface tension; german edition DIN EN 14370; 2004-1 1), and the surface tension of the substrate surface may be determined according to DIN EN ISO 19403-2:2020-04 (wettability-part 2; surface free energy of the solid surface is determined by measuring the contact angle). Without being bound by a particular theory, it is believed that the difference in surface tension contributes at least in part to the coating composition being suitable for application with a precision application device that can apply the coating composition without overspray.

The coating composition may be applied over at least a portion of the substrate, whether uncoated or at least partially with a coating applied thereto, to form a coating, non-limiting examples including primer coatings, basecoats, clearcoats, and topcoats. In addition, any of the coating compositions may be a one-component (1-K), two-component (2-K) or multi-component coating composition.

The substrates on which the coating composition may be applied include a wide range of substrates. For example, the coating composition may be applied to a vehicle substrate, industrial substrate, aerospace substrate, and the like.

As non-limiting examples, the substrate may include a polymer or a composite material, such as a fiberglass composite. Vehicle components, which are typically formed from thermoplastic and thermoset materials, include bumpers and trim pieces.

Non-limiting examples of substrates to which the coating composition may be applied include rigid metal substrates such as ferrous metals, aluminum alloys, copper, and other metal and alloy substrates. The ferrous metal substrate may include iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, acid leached steel, zinc-iron alloys, and combinations thereof. Combinations or composites of ferrous and non-ferrous metals may also be used.

Non-limiting examples of steel substrates (such as cold rolled steel or any of the steel substrates listed above) include those coated with a weldable, zinc-rich or iron phosphide-rich organic coating. Cold rolled steel may also be suitable when pretreated with suitable solutions known in the art, such as metal phosphate solutions, aqueous solutions containing group IIIB or group IVB metals, organophosphate solutions, organophosphonate solutions, and combinations thereof, as discussed below. Non-limiting examples of aluminum alloys include those used in the vehicle or aerospace industries, such as 2000, 6000 or 7000 series aluminum; 2024. 7075, 6061 are specific examples. The alloys may be uncoated or they may contain a coating on the surface that consists of a different aluminum alloy than the base/bulk alloy below the coating.

Non-limiting examples of substrates include more than one metal or metal alloy, as the substrate may be a combination of two or more metal substrates assembled together, such as hot dip galvanized steel assembled with an aluminum substrate.

Non-limiting examples of the shape of the metal substrate include a sheet, plate, bar, or any desired shape form, but in many cases it may be in the form of a vehicle component such as a body, door, trunk lid, fender, hood, or bumper. The thickness of the substrate may vary as desired.

When there is no intermediate coating between the substrate and the coating composition, the coating may be applied directly to the metal substrate. This means that the substrate may be bare, as described below, or may be treated with a pretreatment composition as described below, but the substrate is not coated with any coating composition, such as an electrodepositable composition or a primer composition, prior to application of the curable film-forming composition described in Tu Benwen.

As described above, the substrate used may be a bare metal substrate, in other words, a virgin metal substrate that has not been treated with any pretreatment composition (such as conventional phosphating baths, heavy metal rinse solutions, etc.). In addition, the bare metal substrate that may be used herein may be the cut edge of a substrate that has been otherwise treated and/or coated on the remainder of the substrate surface. Alternatively, the substrate may be subjected to treatment steps known in the art prior to application of the coating composition.

Conventional cleaning procedures and materials may be used to clean the substrate. Non-limiting examples include weakly or strongly alkaline cleaners, such as those commercially available and conventionally used in metal pretreatment processes. Such cleaners are typically after and/or before the water rinse. The metal surface may also be rinsed with an acidic aqueous solution after or in lieu of alkaline cleaner cleaning. Non-limiting examples of rinse solutions include weakly acidic or strongly acidic cleaners such as dilute nitric acid solutions that are commercially available and are conventionally used in metal pretreatment processes.

According to the compositions, methods, systems and substrates herein, at least a portion of the cleaned aluminum substrate surface may be mechanically or chemically deoxidized, in other words, oxide layers found on the substrate surface are removed to promote uniform deposition of the pretreatment composition (as described below), as well as to promote adhesion of the pretreatment composition coating to the substrate surface. Non-limiting examples of suitable deoxidizers include mechanical deoxidizers, which may uniformly roughen the substrate surface, such as by using a scrubbing or cleaning pad, non-limiting examples of which include nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid, and ammonium bifluoride, or amyhem 7/17 deoxidizers (available from Henkel Technologies, madison Heights, mich.), oakit deoxidizer LNC (available from Chemetall), TURCO deoxidizer 6 (available from Henkel), or combinations thereof. Typically, the chemical deoxidizer comprises a carrier, typically an aqueous medium, such that the deoxidizer may be in the form of a solution or dispersion in the carrier, in which case the solution or dispersion may be contacted with the substrate by any of a variety of known techniques, such as dip coating or immersion, spray coating, intermittent spray coating, post-dip coating, post-spray coating, brush coating, or roll coating.

The coating compositions described herein may include an adhesion promoter. Specific adhesion promoters may be selected for the preferred properties of a particular substrate, non-limiting examples being metals or plastics. In a non-limiting example, the adhesion promoter includes a free acid, which may include organic and/or inorganic acids, that are included as separate components of the coating composition, rather than any acid that may be used to form a polymer that may be present in the coating composition. The free acid may include tannic acid, gallic acid, phosphoric acid, phosphorous acid, citric acid, malonic acid, derivatives thereof, or mixtures thereof. Suitable derivatives include esters, amides and/or metal complexes of such acids. Typically, the free acid comprises phosphoric acid, such as 100% orthophosphoric acid, superphosphoric acid, or an aqueous solution thereof, such as a 70% to 90% phosphoric acid solution. Another non-limiting example of an adhesion promoter that may be used, particularly on plastic substrates, is disclosed in U.S. patent application publication No. 2022/0154007. Non-limiting examples of other suitable adhesion promoting components include metal phosphates, organic phosphates, and organic phosphonates, as well as metal phosphates including zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, cobalt phosphate, zinc-iron phosphate, zinc-manganese phosphate, zinc-calcium phosphate. Other non-limiting examples of adhesion promoters include phosphorylated epoxy resins, which may include the reaction product of an epoxy-functional material with a phosphorous-containing material. Further non-limiting examples of adhesion promoters include alkoxysilane adhesion promoters such as acryloxyalkoxysilane such as gamma-acryloxypropyl trimethoxysilane and methacryloxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl methyl dimethoxy silane, 3-acryloxypropyl trimethoxysilane, vinyl triethoxysilane, p-styryl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, gamma-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, gamma-aminopropyl trimethoxysilane, 3-aminopropyl triethoxy silane, N-2 (aminoethyl) 3-amino-propyl methyl dimethoxy silane, N-2 (aminoethyl) 3-amino-propyl trimethoxysilane, N-2 (aminoethyl) 3-aminopropyl triethoxy silane, 3-aminopropyl methyl dimethoxy silane, 3-mercaptopropyl trimethoxysilane and siloxane borates.

As a non-limiting example, the vehicle substrate may include a component of a vehicle. Suitable vehicles may include land vehicles such as, for example, animal trailers (e.g., horse trailers), automobiles, trucks, buses, vans, heavy equipment, golf carts, motorcycles, bicycles, trains, railroad vehicles, and the like. The vehicle may also include a watercraft such as, for example, a ship, a vessel, a shipping container, a hovercraft, and the like. The vehicle substrate may include components of the body of the vehicle, such as a motor vehicle hood, door, trunk, roof, etc.; wings, fuselages, etc., such as aircraft or spacecraft; such as a hull or the like.

As non-limiting examples, the substrate may include an aerospace substrate (a component of an aerospace vehicle, such as an aircraft, such as, for example, an aircraft (e.g., a private aircraft, and small, medium, or large commercial passenger, cargo, military aircraft, rockets, and other spacecraft), a helicopter (e.g., a private, commercial, and military helicopter).

The coating composition may be applied to industrial substrates, which may include tools, heavy equipment, furniture such as office furniture (e.g., office chairs, tables, filing cabinets, etc.), appliances such as refrigerators, ovens and ranges, dishwashers, microwave ovens, washing machines, dryers, small appliances (e.g., coffee machines, slow cookers, pressure cookers, blenders, etc.), metal equipment, extruded metals such as extruded aluminum for window frames, other indoor and outdoor metal building materials, and the like.

The coating composition can be applied to storage tanks, windmills, nuclear power plants, packaging substrates, wooden floors and furniture, clothing, electronic equipment (including housings and circuit boards), glass and transparencies, sports equipment (including golf balls), stadiums, buildings, bridges, and the like.

Nonmetallic substrates include, but are not limited to, polymeric substrates such as polyesters, polyolefins, polyamides, cellulosics, polystyrenes, polyacrylic acids, poly (ethylene naphthalate), polypropylene, polyethylene, nylon, ethylene vinyl alcohol (EVOH), polylactic acid (PLA), other "green" polymeric substrates, poly (ethylene terephthalate) (PET), polycarbonates, polycarbonate acrylonitrile butadiene styrene (PC/ABS), polyamides, and/or plastic composites: substrates such as: glass or carbon fiber composites. The nonmetallic substrate may include wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, synthetic and natural textile leather, and the like

The coating composition may be applied by any means such as spraying, electrostatic spraying, dipping, roller brushing, immersing, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, rolling, and the like. The coating composition may also be applied with a precision application device that can apply the coating composition without any overspray. Thus, such devices can apply the coating composition to a substrate that is not masked with a removable material (such as, for example, a tape material). The properties of the coating compositions described herein used in combination with the precision application device may enable the coating composition to be applied over at least a portion of a substrate without overspray.

An application device that applies the coating composition without overspray may be used to create the desired pattern and/or design on the substrate. As a non-limiting example, these application devices can apply the coating composition in a single pass without masking the substrate to produce two or more colors on different portions of the substrate

Non-limiting examples of devices that can apply the coating composition without overspray include devices that apply the composition as a continuous jet, as continuous droplets, and/or as drop-on-demand. Specific non-limiting examples of such devices include piezoelectric actuated valve ejectors, air actuated valve ejectors, continuous inkjet printers, gas jet drop generators, vibrating tip drop generators, piezoelectric actuated micro-pneumatic drop generators, and electrohydrodynamic drop generators.

The applicator may be a high transfer efficiency applicator that includes a nozzle that includes an opening. The high transfer efficiency applicator may include more than one or more nozzles. The nozzle opening may have any suitable shape, non-limiting examples being circular, oval, square and rectangular. The nozzle may include a channel having the same cross-sectional shape and size as the opening. The nozzle opening may have a diameter of at least 25 μm, such as at least 50 μm and at least 75 μm, and may be at most 300 μm, such as at most 275 μm, at most 250 μm, at most 225 μm and at most 200 μm, and may be 25 μm to 300 μm, such as 25 μm to 250 μm, 25 μm to 200 μm, 50 μm to 300 μm, 50 μm to 250 μm, 50 μm to 200 μm, 75 μm to 300 μm, 75 μm to 250 μm and 75 μm to 200 μm. The nozzle opening may be any of the above values or a range between any of the above values (and including the values). The droplets or streams emitted from the nozzles may have the same diameter as the nozzle openings.

The droplet diameter can be determined using JetXpert Dropwatcher available from ImageXpert, inc. And its present analytical function now functioning in a double pulse mode. Also, the nozzle inspector feature of JetXpert may be used to determine the nozzle diameter.

The coating composition may be provided to the applicator under pressure. In many cases, the plurality of nozzles each include a cylindrical passage having the same diameter as the nozzle opening. The combination of pressure and channel dimensions causes a shear stress to be applied to the coating composition. The shear-thinning properties of the coating composition as described above allow the coating composition to be discharged from the nozzle at a desired flow rate or droplet rate.

The flow or droplet rate may be at least 25cc/min, such as at least 50cc/min and at least 75cc/min, and may be at most 300cc/min, such as at most 275cc/min, at most 250cc/min, at most 225cc/min, and at most 200cc/min, and may be 25cc/min to 300cc/min, such as 50cc/min to 300cc/min, 75cc/min to 300cc/min, 25cc/min to 250cc/min, 50cc/min to 250cc/min, 75cc/min to 250cc/min, 25cc/min to 200cc/min, 50cc/min to 200cc/min, and 75cc/min to 200cc/min. When the flow rate or droplet rate is too low, the coating may not have the desired properties. If the flow or drop rate is too high, the coating may be prone to puddling and/or sagging. The flow rate or droplet rate may be any of the values described above or a range between any of the values described above (and including such values).

The coating compositions described herein have high transfer efficiency when applied according to the methods and systems described herein, in other words, most, if not all, of the coating composition is applied to the substrate after exiting the applicator and is not wasted and/or oversprayed. The transfer efficiency of the coating composition may be at least 90wt.%, such as at least 91wt.%, at least 92wt.% and at least 93wt.%, and may be at most 100wt.%, such as at most 99wt.% and at most 98wt.%, and may be from 90% to 100%, such as from 92% to 100% and from 93 to 99%. The transfer efficiency of the coating composition may be any of the values described above or ranges between any of the values described above (and including such values).

Transfer efficiency may be enhanced by placing the applicator in close proximity to the substrate. Thus, the distance from the nozzle tip in the applicator to the substrate may be at least 0.5cm, such as at least 0.6cm and at least 0.75cm, and may be at most 5cm, at most 4cm and at most 3cm, and may be 0.5cm to 5cm, such as 0.5cm to 4cm, 0.5cm to 3cm, 0.75cm to 5cm, 0.75cm to 4cm and 0.75 to 3cm. The distance from the applicator to the substrate may be any of the values described above or a range between any of the values described above (and including such values).

The high transfer efficiency of the coating composition and the close proximity of the applicator to the substrate can minimize any evaporation of volatile components of the coating composition when applied to the substrate. The total solids of the applied coating composition may be within at least 10wt.%, such as at least 7.5wt.% and at least 5wt.%, and may be within 1wt.%, such as 2wt.% and 3wt.% of the total solids of the coating composition entering the applicator. Typically, there is no loss of volatile components and the composition of the applied coating composition is the same as the coating composition entering the applicator. The total solids of the applied coating composition may be any one of the values above or a range between any of the values above (and including the value) as compared to the total solids of the coating composition entering the applicator.

As noted above, applicators suitable for use with the methods and systems described herein and useful for coating compositions may include a plurality of nozzles. The number of nozzles on the applicator may be at least one, such as at least 5 and at least 10, and may be at most 3,000, such as at most 2,700, at most 2,250, at most 2,000, at most 1,500, at most 1,000, at most 500, at most 100, at most 75, at most 70, and at most 65, and may be 5 to 1,000, such as 10 to 500, and 10 to 100. The number of nozzles included in the applicator may be any one of the values described above or a range between any of the values described above (and including the values).

Depending on the number of nozzles included on the applicator, the applicator may have a path width of at least 0.5cm, such as at least 1cm, at least 2.5cm, and at least 5cm, and may be at most 15cm, such as at most 14cm, at most 13cm, and at most 12cm, and may be 1cm to 15cm, such as 2.5cm to 14cm, and 5cm to 15 cm. The path width of the coating composition may be any of the above values or a range between any of the above values (and including the values).

Due to the high transfer efficiency, rheological profile of the coating composition, and use of the high efficiency applicator described herein, there is minimal or no overlap between the passage of the applicator within the target area or target deposition path.

Due to the high transfer efficiency, rheological profile of the coating composition, and use of the high efficiency applicator described herein, the applicator is able to pass relatively quickly through the substrate in a target area or target deposition path. Thus, the applicator may have a tip speed of at least 50mm/sec, such as at least 100mm/sec and at least 200mm/sec, and may be at most 1000mm/sec, such as at most 750mm/sec and at most 500mm/sec, and may be 50mm/sec to 1000mm/sec, such as 50mm/sec to 750mm/sec, 50mm/sec to 500mm/sec, 100mm/sec to 1000mm/sec, 100mm/sec to 750mm/sec, 100mm/sec to 500mm/sec, 200mm/sec to 1000mm/sec, 200mm/sec to 750mm/sec, and 200mm/sec to 500mm/sec. The tip speed of the applicator may be any of the values described above or a range between any of the values described above (and including such values).

The coating composition may be applied directly to a substrate and provided as a primer coating. Additionally, the coating composition may be applied as a basecoat, and the basecoat may include a colorant. Furthermore, the coating composition may be a clear coat that may cover at least a portion of any of the coatings described herein. The coating compositions described herein may be a final coating or a top coating that covers at least a portion of the coatings described herein.

At least one or more of the above-described coatings may be included in the coating compositions described herein according to the various systems, methods, and coating compositions described herein.

Coatings that do not include the coating compositions described herein ("other coatings"), the methods and/or systems described herein may include various coatings applied by various methods known in the art. As non-limiting examples, the other coating may be a water-based coating, a powder coating, and/or a galvanic coating as known in the art. Other coatings may be applied using conventional brush, roller, spray, and electrocoat techniques.

The coating composition may be free or substantially free of cross-linking agents. Such coating compositions may be 1-K or single package coating compositions. Typically, the 1-K coating composition is dried after application to a substrate.

When the coating composition needs to be dried after application to a substrate, the drying may be performed under ambient conditions. The coating composition may be dried after application to the substrate at a temperature of at least 20 ℃, such as at least 25 ℃, at least 30 ℃, and at least 35 ℃, and may be up to 140 ℃, such as up to 120 ℃, up to 100 ℃, up to 80 ℃, up to 70 ℃, and up to 60 ℃, and 20 ℃ to 140 ℃, such as 25 ℃ to 120 ℃, and 30 ℃ to 100 ℃. The coating composition may be dried at or between any of the above temperatures (and including such temperatures).

The time period for drying the coating composition is a specified time period for removing volatile components from the coating composition, and does not include the time required to transfer the coating composition to another step (such as a curing step) and to subject the coating composition to another step (such as a curing step). The period of time for drying generally depends on the composition of the coating composition and the drying temperature employed. As a non-limiting example, the coating composition is allowed to flash for 10 minutes before curing. As a non-limiting example, moisture curing for single package (1-K) coating compositions takes 2 hours to reach touch drying.

When the coating compositions disclosed herein require curing, the coating compositions can be cured at ambient conditions and can be cured at temperatures of at least 20 ℃, such as at least 22 ℃ and at least 25 ℃, and can be cured at temperatures of at most 270 ℃, such as at most 260 ℃, at most 225 ℃, at most 200 ℃, at most 175 ℃, at most 140 ℃, at most 120 ℃, at most 100 ℃, at most 90 ℃, at most 80 ℃, and at most 70 ℃, and at temperatures of 20 ℃ to 270 ℃, such as 22 ℃ to 270 ℃ and 25 ℃ to 270 ℃, 20 ℃ to 225 ℃, 22 ℃ to 225 ℃, and 25 ℃ to 225 ℃. The curing temperature for the coating composition may be any of the values described above or ranges between any of the values described above (and including such values). The coating composition may be cured at the temperature for a period of at least 5 seconds, such as at least 10 seconds, at least 30 seconds, at least 45 seconds, at least 1 minute, at least 2 minutes, at least 3 minutes, at least 4 minutes, and at least 5 minutes, and may be up to 40 minutes, such as up to 30 minutes, up to 20 minutes, and up to 15 minutes, and 5 seconds to 40 minutes, such as 10 seconds to 30 minutes, 1 minute to 20 minutes, 5 minutes to 30 minutes, 1 minute to 20 minutes, and 5 minutes to 20 minutes. The period of time for curing generally depends on the temperature used for curing. The time period for curing the coating composition is a specified time period for curing and does not include the time required to transfer the coating composition to another step and to subject the coating composition to another step. The amount of time required to cure the coating composition may be any of the values described above or ranges between any of the values described above (and including such values).

After the applied coating composition is cured and/or dried, it provides a coating on the substrate. The thickness of the coating, referred to as dry film thickness, may be at least 0.5 μm, such as at least 1 μm, at least 2 μm, at least 5 μm and at least 7 μm, and may be at most 65 μm, such as at most 60 μm, at most 55 μm and at most 52 μm, and 0.5 μm to 60 μm, such as 0.5 μm to 65 μm, such as 0.5 μm to 60 μm, 0.5 μm to 55 μm, 0.5 μm to 52 μm, 1 μm to 65 μm, 1 μm to 60 μm, 1 μm to 55 μm, 5 μm to 65 μm, 5 μm to 60 μm and 5 μm to 55 μm. The dry film thickness of the coating may be any of the values described above or ranges between any of the values described above (and including such values).

Dry film thickness can be measured using Fischerscope MMS Permascope in accordance with ASTM D7091-21 "dry film thickness non-destructive measurement standard practice" for non-magnetic coatings applied to ferrous metals and non-magnetic non-conductive coatings applied to non-ferrous metals.

The coating compositions described herein provide many other good properties acceptable for film properties including, but not limited to, adhesion, scratch resistance, abrasion resistance, gloss, DOI, smoothness (Wa, wb, wc, wd, we, long wave, short wave), moisture resistance, uv resistance, flexibility, stoneware resistance, and color stability.

Examples

Examples 1 to 5

A colored film-forming composition was prepared by combining the ingredients in table 1.

TABLE 1

¹ A dispersion of Aerosil R-812 silica (Degussa Chemicals) in an acrylic polyol, as in example A of US5959040, was prepared at a solids 4.4:1 acrylic to Si ratio.

² Hindered amine light stabilizers, available from Mayzo inc.

³ Benzotriazole uv absorbers are available from Chitec Technology.

⁴ Benzotriazole uv absorbers are available from Everlight Chemical Taiwan.

⁵ Nonionic defoamers, available from Kusumoto ChemThe icals LTD.

⁶ Polyether modified polysiloxanes, available from Byk Additives.

⁷ SCA in acrylic polyols is available from Allnex.

⁸ Melamine formaldehyde resins, available from Ineos.

⁹ An adhesion promoter, as prepared in example G of U.S. patent No. 7,329,468.

¹⁰ Acrylic resins, e.g. as prepared in example A of U.S. Pat. No. 5,646,214

¹¹ Acrylic microgels as prepared in example a of us patent No. 10,370,555.

¹² Urethane resins, as prepared in example B of U.S. Pat. No. 5,646,214

¹³ Polydimethylsiloxane oils are available from Dow Corning.

³⁷ Diisopropanolamine

³⁸ Dodecyl benzyl sulfonic acid

The compositions of examples 1-5 were precisely applied to panels coated with Kino 1209 (a clear coating commercially available from PPG Kansai Automotive Finishes (having a surface energy of 27.5 mN/m)) using a Durr Ecopantjet applicator and application conditions as in Table 2 (some physical properties of the compositions are also shown). Viscosity and percent recovery (% recovery) were measured using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with DG26.7 measurement system. Surface tension such as German version EN 14370;2004; 2004-1.

TABLE 2

After flashing at 23 ℃ for 10min, the panel was cured at 140 ℃ for 30 min. The visual test results are shown in table 3, where visual rank is best > better > worse.

TABLE 3 Table 3

Examples 2 to 5 show a better combination of horizontal and vertical appearances than example 1.

Example 6

The coating compositions were prepared by combining the components in the amounts identified in table 4.

TABLE 4 Table 4

¹⁴ 3074, commercially available from The Dow Chemical Company. />

¹⁵ OFS-6070 silane is commercially available from Dow Corning.

¹⁶ Foamex N, commercially available from Evonik.

¹⁷ RE-610E, commercially available from Solvay.

¹⁸ BYK-307 is commercially available from BYK.

¹⁹ 14, commercially available from Birla Carbon.

²⁰ RSN-0409HS is commercially available from The Dow Chemical Company.

²¹ 6900-20X, commercially available from Kusumoto Chemicals.

²² OFS-6194 silane is commercially available from Dow Corning.

²³ OFS-6341 silane, commercially available from Dow Corning.

²⁴ KBM-403SILANE, commercially available from Shin Etsu.

²⁵ 292, commercially available from BASF.

²⁶ 1130, commercially available from BASF.

²⁷ KBE-903SILANE, commercially available from Shin Etsu.

²⁸ NEOSTANN U-220H, commercially available from Nitto Kasei Co., ltd.

The coating composition (75% solids by volume) was applied to a substrate and cured at ambient conditions using a Rea Jet DOD 2.0 applicator with 32 nozzles and dried to the touch after two hours and dried after 9 hours. The test results and visual effects (methods described above) are shown in table 5.

TABLE 5

% solids at application (by volume)	75
		Low shear viscosity (cps, 0.1 s) ^-1 ) And 25 DEG C	6179
High shear viscosity (cps, 1000 s) ^-1 ) And 25 DEG C	109
		Recovery%	88.6
Tip speed (mm/sec)	500
		Printhead angle (°)	15
Target distance (mm)	5
		Horizontal appearance	Good quality
Vertical sagging	Minimum of
		Dry film thickness (μm)	40

Example 7

The 2k isocyanate formulations were prepared as in table 6 (in grams) and applied to ED-6670 panels available from ACT Test Panels LLC using a Durr ecopiantjet precision 64 nozzle applicator.

TABLE 6

²⁹ Tinuvin 928, available from BASF

³⁰ Available from BASF

³¹ Polyacrylic acid polymer solutions, obtainable from BYK Additives and Instruments

³² Polyether modified polydimethylsiloxanes, obtainable from BYK Additives and Instruments

³³ Adhesion promoters, as manufactured in example C of US 7329468

³⁴ Melamine formaldehyde resins, obtainable from Allnex

³⁵ Polyester polyol resins such as those produced in example 3 of U.S. patent No. 6,228,953.

³⁶ Polyfunctional isocyanates, obtainable from BASF

³⁷ Diisopropanolamine

³⁸ Dodecyl benzyl sulfonic acid

Using the visual effects and methods described above, the properties and application properties are shown in Table 7.

TABLE 7

% solids at application	58.4
		Low shear viscosity (cps, 0.1 s) ^-1 ) And 25 DEG C	5661
High shear viscosity (cps, 1000 s) ^-1 ) And 25 DEG C	116
		Recovery%	94
Flow rate (cc/min)	200
		Tip speed (mm/sec)	700
Target distance (mm)	15
		Jet stability	Is that
Horizontal appearance	Good quality
		Vertical sagging	Minimum of
Dry film thickness (μm)	42

Example 8

Colored film-forming compositions were prepared by combining the ingredients in table 8 (superscript as in table 1).

TABLE 8

² Hindered amine light stabilizers, available from Mayzo inc.

³ Benzotriazole uv absorbers are available from Chitec Technology.

⁴ Benzotriazole uv absorbers are available from Everlight Chemical Taiwan.

⁵ Nonionic defoamers are available from Kusumoto Chemicals LTD.

⁷ SCA in acrylic polyols is available from Allnex.

⁸ Melamine formaldehyde resins, available from Ineos.

¹⁰ Acrylic resins, e.g. as prepared in example A of U.S. Pat. No. 5,646,214

¹¹ Acrylic microgels as prepared in example a of us patent No. 10,370,555.

¹² Urethane resins, as prepared in example B of U.S. Pat. No. 5,646,214

¹³ Polydimethylsiloxane oils are available from Dow Corning.

³⁷ Di-isoPropanolamine

³⁸ Dodecyl benzyl sulfonic acid

The compositions of example 8 and comparative compositions made according to example 1 table 1 were precisely applied to panels coated with Kino 1209 (a clear coating commercially available from PPG Kansai Automotive Finishes (having a surface energy of 27.5 mN/m)) using a Durr ecopiantjet applicator and application conditions as in table 9 (some physical properties of the compositions are also shown). Viscosity and percent recovery (% recovery) were measured using an Anton Paar MCR 301 rheometer with a double gap cylinder equipped with DG26.7 measurement system. Surface tension such as German version EN 14370;2004; 2004-1. The performance attributes (table 10) are compared to the comparative compositions.

TABLE 9

	Example 8
		% solids at application	51.5
Low Shear Viscosity (LSV) cps,0.1s ^-1 And 25 DEG C	5957
		High Shear Viscosity (HSV) cps,1000s ^-1 And 25 DEG C	69
Recovery%	106
		Surface tension (mN/m)	26
Flow rate (cc/min)	220
		Distance (mm)	20
Tip speed (mm/sec)	700

After flashing at room temperature for 10min, the panels were cured at 140 ℃ for 30 min. The visual test results are shown in table 10.

Table 10

	Example 8
		Jet stability	Is that
Horizontal appearance	Preferably
		Vertical sagging	Preferably, it is
60-degree sagging	Good quality
		Wetting the clear coat with 27.5mN/m	Good quality
Dry film thickness (um)	52

Although specific embodiments of the disclosure have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous variations of the details of the disclosure can be made without departing from the scope of the appended claims.

Claims

1. A coating composition comprising an organic solvent:

wherein the coating composition has a shear-thinning rheology profile;

wherein at high shear rates, the coating composition has a viscosity low enough to flow through the openings in the high efficiency applicator and be applied to a surface; and is also provided with

Wherein the coating composition has a viscosity of 1,000cps to 30,000cps at 25 ℃ with or without shear.

2. The coating composition of claim 1, comprising an amount of organic solvent of 5wt.% to 90wt.%, such as 5wt.% to 85wt.%, 5wt.% to 80wt.%, 5wt.% to 75wt.%, 5wt.% to 70wt.%, 10wt.% to 90wt.%, such as 10wt.% to 85wt.%, 10wt.% to 80wt.%, 10wt.% to 75wt.%, 10wt.% to 70wt.%, 20wt.% to 90wt.%, 20wt.% to 85wt.%, 20wt.% to 80wt.%, 20wt.% to 75wt.%, 30wt.% to 90wt.%, 30wt.% to 85wt.%, 30wt.% to 80wt.%, 30wt.% to 75wt.%, 30wt.% to 70wt.%, 40wt.% to 90wt.%, 40wt.% to 85wt.%, 40wt.% to 80wt.%, 40wt.% to 75wt.%, and 40wt.% to 70wt.%, based on the weight of the coating composition.

3. The coating composition of any one of claims 1 or 2, comprising a total amount of solids of 10wt.% to 95wt.%, such as 10wt.% to 90wt.%, 10wt.% to 80wt.%, 10wt.% to 75wt.%, 10wt.% to 70wt.%, 15wt.% to 95wt.%, 15wt.% to 90wt.%, 15wt.% to 80wt.%, 15wt.% to 75wt.%, 15wt.% to 70wt.%, 20wt.% to 100wt.%, 20wt.% to 90wt.%, 20wt.% to 80wt.%, 20wt.% to 75wt.%, 25wt.% to 70wt.%, 25wt.% to 90wt.%, 25wt.% to 75wt.%, 25wt.% to 70wt.%, 30wt.% to 100wt.%, 30wt.% to 90wt.%, 30wt.% to 80wt.%, 30wt.% to 75wt.%, and 30wt.% to 70wt.%, based on the weight of the coating composition determined according to ASTM D2369 (2015).

4. The coating composition of any one of claims 1 to 3, wherein the organic solvent in the volatile content of the coating composition is 70wt.% to 100wt.%, such as 70wt.% to 95wt.%, 70wt.% to 90wt.%, 72.5wt.% to 100wt.%, 72.5wt.% to 95wt.%, 72.5wt.% to 90wt.%, 75wt.% to 100wt.%, 75wt.% to 95wt.%, and 75wt.% to 90wt.% based on the weight of the volatile components in the coating composition.

5. The coating composition according to any one of claims 1 to 4 having a viscosity of at 0.1s measured at 25 ℃ using an Anton Paar MCR 301 rheometer with a double gap measuring cylinder equipped with DG26.7 measurement system ^-1 And a viscosity of 1,000 to 30,000cps, such as 1,000 to 25,000cps, 1,000 to 20,000cps, 1,000 to 15,000cps, 2,000 to 30,000cps, 2,000 to 20,000cps, 2,000 to 15,000cps, 3,000 to 30,000cps, 3,000 to 25,000cps, 3,000 to 20,000cps, 3,000 to 15,000cps, 4,000 to 30,000cps, 4,000 to 25,000cps, 4,000 to 20,000cps, and 4,000 to 15,000 cps.

6. The coating composition according to any one of claims 1 to 5, wherein Anton Paar with a double gap measuring cylinder equipped with DG26.7 measurement system is used at 25 ℃ MCR 301 rheometer for 1000s ^-1 The lower viscosity is 25 to 150cps, such as 25 to 140cps, 25 to 130cps, 25 to 125cps, 35 to 150cps, 35 to 140cps, 35 to 130cps, 35 to 125cps, 40 to 150cps, 40 to 140cps, 40 to 130cps, 40 to 125cps, 45 to 150cps, 45 to 140cps, 45 to 130cps, and 45 to 125cps.

7. The coating composition according to any one of claims 1 to 6, wherein the measurements are carried out at 25 ℃ using an Anton Paar MCR 301 rheometer with a double gap measuring cylinder equipped with DG26.7 measurement system, at 0.1s ^-1 The viscosity measured at 1000s ^-1 The viscosity of the coating composition measured below is 6 to 1,200 times, such as 6 to 1,000 times, 6 to 750 times, 6 to 500 times, 6 to 350 times, 10 to 1,200 times, 10 to 1,000 times, 10 to 750 times, 10 to 500 times, 10 to 350 times, 20 to 1,200 times, 20 to 1,000 times, 20 to 750 times, 20 to 500 times, 20 to 350 times, 30 to 1,200 times, 30 to 1,000 times, 30 to 750 times, 30 to 500 times, 30 to 350 times, 40 to 1,200 times, 40 to 1,000 times, 40 to 750 times, 40 to 500 times, and 40 to 350 times.

8. The coating composition according to any one of claims 1 to 7, wherein the coating composition is a one-component composition.

9. The coating composition of any one of claims 1 to 7, wherein the coating composition is a multi-component composition comprising a first component and a second component.

10. The coating composition of claim 9, wherein first and second components are combined prior to flowing through the opening in the high efficiency applicator.

11. The coating composition of any one of claims 1 to 10, wherein the coating composition is free of a colorant.

12. The coating composition of any one of claims 1 to 10, wherein the coating composition comprises 0.5wt.% to 40wt.%, such as 0.15wt.% to 38wt.%, and 1wt.% to 34wt.% of a colorant, based on the weight of the coating composition.

13. The coating composition of any one of claims 1 to 12, wherein the coating composition comprises 0.1wt.% to 25wt.%, such as 0.2wt.% to 25wt.%, 0.5wt.% to 25wt.%, 0.75wt.% to 25wt.%, 1wt.% to 25wt.%, 0.1wt.% to 15wt.%, 0.2wt.% to 15wt.%, 0.5wt.% to 15wt.%, 0.75wt.% to 15wt.%, 1wt.% to 15wt.%, 0.1wt.% to 10wt.%, 0.2wt.% to 10wt.%, 0.5wt.% to 10wt.%, 0.75wt.% to 10wt.%, and 1wt.% to 10wt.% of a rheology modifier, based on the weight of the coating composition.

14. The coating composition of any one of claims 1 to 13, wherein the coating composition comprises a combination of materials comprising insoluble spheres, low density non-porous particles, and insoluble needle-like or rod-like crystals.

15. The coating composition of claim 14 wherein the insoluble spheres are selected from the group consisting of super crosslinked polymeric microspheres, highly crosslinked acrylic polymer particles, and crosslinked hydroxy functional polyacrylic resins.

16. The coating composition according to any one of claims 14 or 15, wherein the low density non-porous particles are selected from fumed silica and clay.

17. The coating composition according to any one of claims 14 to 16, wherein the insoluble needle-like or rod-like crystals are selected from natural gums, calcites, organic transition metal complexes, reaction products of amines and/or polyamines with polyisocyanates and reaction products of aromatic amines with polyisocyanates.

18. The coating composition of any one of claims 14 to 17, wherein the amount of insoluble spheres is 0.1wt.% to 5wt.%, such as 0.25wt.% to 5wt.%, 0.5wt.% to 5wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.%, 0.5wt.% to 3wt.%, based on the weight of the coating composition.

19. The coating composition of any one of claims 14 to 18, wherein the amount of low density non-porous particles is 0.1wt.% to 5wt.%, such as 0.25wt.% to 5wt.%, 0.5wt.% to 5wt.%, 0.1wt.% to 4wt.%, 0.25wt.% to 4wt.%, 0.5wt.% to 4wt.%, 0.1wt.% to 3wt.%, 0.25wt.% to 3wt.%, 0.5wt.% to 3wt.%, based on the weight of the coating composition.

20. The coating composition of any one of claims 14 to 19, wherein the amount of insoluble needle-like or rod-like crystals is 0.1 to 5wt.%, such as 0.25 to 5wt.%, 0.5 to 5wt.%, 0.1 to 4wt.%, 0.25 to 4wt.%, 0.5 to 4wt.%, 0.1 to 3wt.%, 0.25 to 3wt.%, 0.5 to 3wt.%, based on the weight of the coating composition.

21. The coating composition according to any one of claims 14 to 20, wherein the primary particle size (Dv ₅₀ ) From 0.1 μm to 15 μm, such as from 0.1 μm to 10 μm, from 0.1 μm to 7.5 μm, from 0.1 μm to 5 μm, from 0.5 μm to 15 μm, from 0.5 μm to 10 μm, from 0.5 μm to 7.5 μm, from 0.5 μm to 5 μm, from 1 μm to 15 μm, from 1 μm to 10 μm, from 1 μm to 7.5 μm, and from 1 μm to 5 μm, as measured using a Malvern Zetasizer dynamic light scattering instrument.

22. The coating composition according to any one of claims 14 to 21, wherein the particle size (Dv ₅₀ ) From 0.1 μm to 1.2 μm as measured by a Malvern Zetasizer dynamic light scattering instrument.

23. The coating composition of any one of claims 1 to 22, wherein the coating composition comprises 0.1 to 70wt.%, such as 0.5 to 70wt.%, 1 to 70wt.%, 5 to 70wt.%, 10 to 70wt.%, 15 to 70wt.%, 20 to 70wt.%, 1 to 60wt.%, 5 to 60wt.%, 10 to 60wt.%, 15 to 60wt.%, 20 to 60wt.%, 1 to 50wt.%, 5 to 50wt.%, 10 to 50wt.%, 15 to 50wt.%, and 20 to 50wt.% of film-forming resin, based on the weight of the coating composition.

24. The coating composition of any one of claims 1 to 23, wherein the coating composition is a thermosetting composition.

25. A method of forming a coating on at least a portion of a substrate, the method comprising:

applying the coating composition of claims 1 to 24 to flow through an applicator;

the applicator includes a nozzle;

The nozzle being capable of imparting a shear stress to the coating composition;

the coating composition exhibits low viscosity as it flows through the nozzle;

the coating composition forms discrete droplets upon exiting the nozzle; and

the droplets combine to form a coating upon contact with the substrate.

26. A method of forming a coating on at least a portion of a substrate, the method comprising:

the applicator includes a nozzle;

the coating composition exhibits low viscosity as it flows through the nozzle;

the coating composition forms a stream upon exiting the nozzle; and

the streams combine to form a coating upon contact with the substrate.

27. The method according to claim 25, wherein the diameter of the droplet determined using JetXpert Dropwatcher available from ImageXpert and the present analysis function in double pulse mode is 25 to 300 μm, such as 25 to 250 μm, 25 to 200 μm, 50 to 300 μm, 50 to 250 μm, 50 to 200 μm, 75 to 300 μm, 75 to 250 μm and 75 to 200 μm.

28. The method according to claim 26, wherein the diameter of the flow determined using JetXpert Dropwatcher available from ImageXpert and the present analysis function in double pulse mode is 25 to 300 μm, such as 25 to 250 μm, 25 to 200 μm, 50 to 300 μm, 50 to 250 μm, 50 to 200 μm, 75 to 300 μm, 75 to 250 μm and 75 to 200 μm.

29. The method of any one of claims 25 to 28, wherein the coating composition has a transfer efficiency of 90% to 100%.

30. The method of any one of claims 25 to 29, wherein the distance from the applicator to the substrate is from 0.5cm to 5cm, such as from 0.5cm to 4cm, from 0.5cm to 3cm, from 0.75cm to 5cm, from 0.75cm to 4cm, and from 0.75cm to 3cm.

31. The method of any of claims 25-30, wherein the total solids of the coating composition applied on the substrate is within 10wt.% of the total solids of the coating composition entering the applicator.

32. The method of any one of claims 25 to 31, wherein the applied coating composition has a path width of 1cm to 15cm, such as 2.5cm to 14cm and 5cm to 15 cm.

33. The method of any of claims 25 to 32, wherein there is no overlap with the target deposition path.

34. The method of any one of claims 25 to 33, wherein the flow rate through the applicator is 25cc/min to 300cc/min, such as 50cc/min to 300cc/min, 75cc/min to 300cc/min, 25cc/min to 250cc/min, 50cc/min to 250cc/min, 75cc/min to 250cc/min, 25cc/min to 200cc/min, 50cc/min to 200cc/min, and 75cc/min to 200cc/min.

35. The method of any one of claims 25 to 34, wherein the applicator has a tip speed of 50mm/sec to 1000mm/sec, such as 50mm/sec to 750mm/sec, 50mm/sec to 500mm/sec, 100mm/sec to 1000mm/sec, 100mm/sec to 750mm/sec, 100mm/sec to 500mm/sec, 200mm/sec to 1000mm/sec, 200mm/sec to 750mm/sec, and 200mm/sec to 500mm/sec.

36. The method of any one of claims 25 to 35, wherein the coating is transparent.

37. The method of any one of claims 25 to 35, wherein the coating comprises a colorant.

38. The method of any one of claims 25 to 37, wherein the coating is applied over a clear coating.

39. The method of any one of claims 25 to 37, wherein the coating is applied over a primer coating.

40. The method of any one of claims 25 to 39, wherein the coating is a top coating.

41. The method of any one of claims 25 to 40, wherein the difference in surface energy of the substrate and the surface tension of the coating composition (surface energy of the substrate-surface tension of the coating composition) is greater than 0.

42. The method of any one of claims 25 to 41, wherein the coating is cured.

43. The method of any one of claims 25 to 42, wherein the coating is dry.

44. The method of any one of claims 25 to 43, wherein the recovery time of the coating composition is from 1 second to 100 seconds.

45. The method of any one of claims 25 to 44, wherein the dried coating has a film thickness of 0.5 μm to 60 μm, such as 0.5 μm to 65 μm, such as 0.5 μm to 60 μm, 0.5 μm to 55 μm, 0.5 μm to 52 μm, 1 μm to 65 μm, 1 μm to 60 μm, 1 μm to 55 μm, 5 μm to 65 μm, 5 μm to 60 μm, and 5 μm to 55 μm measured according to ASTM D7091-21.

46. A system for precisely applying a coating composition to at least a portion of a substrate, the system comprising:

the coating composition according to any one of claims 1 to 24; and

A device configured to apply the coating composition on at least a portion of the substrate without overspray.

47. The system of claim 46, wherein the device is configured to produce a desired pattern and/or design on the substrate.

48. The system of any of claims 46 or 47, wherein the device is configured to apply the coating composition as a continuous jet, as continuous droplets, and/or as drop-on-demand.

49. The system of any one of claims 46 to 48, wherein the apparatus is configured to apply the coating composition on the substrate such that when the coating composition is cured to form a coating, the coating has a dry film thickness of 0.5 μιη to 65 μιη, such as 0.5 μιη to 60 μιη, 0.5 μιη to 55 μιη, 0.5 μιη to 52 μιη, 1 μιη to 65 μιη, 1 μιη to 60 μιη, 1 μιη to 55 μιη, 5 μιη to 65 μιη, 5 μιη to 60 μιη, and 5 μιη to 55 μιη.

50. The system of any one of claims 46 to 49, wherein the apparatus is configured to apply the coating composition on the substrate such that when the coating composition is dried to form a coating, the coating has a dry film thickness of 0.5 μιη to 60 μιη, such as 0.5 μιη to 50 μιη, 0.5 μιη to 40 μιη, 0.5 μιη to 25 μιη, 1 μιη to 50 μιη, 1 μιη to 40 μιη, 1 μιη to 25 μιη, 5 μιη to 50 μιη, 5 μιη to 40 μιη, and 5 μιη to 25 μιη.

51. The system of any one of claims 46 to 50, wherein the device is configured to apply the coating composition such that the coating composition has a transfer efficiency of 90% to 100%.

52. The system of any one of claims 46 to 51, wherein the device is configured to apply the coating composition such that a distance from a nozzle tip in an applicator to the substrate is 0.5cm to 5cm, such as 0.5cm to 4cm, 0.5cm to 3cm, 0.75cm to 5cm, 0.75cm to 4cm, and 0.75cm to 3cm.

53. The system of any of claims 46 to 52, wherein the device is configured to apply the coating composition such that total solids of the applied coating composition are within 10wt.% of total solids of the coating composition entering the applicator.

54. The system of any one of claims 46 to 53, wherein the device is configured to apply the coating composition such that the coating composition has a path width of 1cm to 15cm, such as 2.5cm to 14cm and 5cm to 15 cm.

55. The system according to any one of claims 46 to 54, wherein the diameter of the droplet determined using JetXpert Dropwatcher available from ImageXpert and the present analytical function in double pulse mode is 25 μm to 300 μm, such as 25 μm to 250 μm, 25 μm to 200 μm, 50 μm to 300 μm, 50 μm to 250 μm, 50 μm to 200 μm, 75 μm to 300 μm, 75 μm to 250 μm and 75 μm to 200 μm.

56. The system according to any one of claims 46 to 55, wherein the diameter of the continuous jet determined using JetXpert Dropwatcher available from ImageXpert and the present analytical function in double pulse mode is 25 to 300 μm, such as 25 to 250 μm, 25 to 200 μm, 50 to 300 μm, 50 to 250 μm, 50 to 200 μm, 75 to 300 μm, 75 to 250 μm and 75 to 200 μm.

57. The system of any one of claims 46 to 56, wherein the apparatus is configured to apply the coating composition such that there is no overlap with a target deposition path.

58. The system of any one of claims 46 to 57, wherein the device is configured to apply the coating composition such that a flow rate through the applicator is 25cc/min to 300cc/min, such as 50cc/min to 300cc/min, 75cc/min to 300cc/min, 25cc/min to 250cc/min, 50cc/min to 250cc/min, 75cc/min to 250cc/min, 25cc/min to 200cc/min, 50cc/min to 200cc/min, and 75cc/min to 200cc/min.

59. The system of any one of claims 46 to 58, wherein the device is configured to apply the coating composition such that application Tu Qiju has a tip speed of 50mm/sec to 1000mm/sec, such as 50mm/sec to 750mm/sec, 50mm/sec to 500mm/sec, 100mm/sec to 1000mm/sec, 100mm/sec to 750mm/sec, 100mm/sec to 500mm/sec, 200mm/sec to 1000mm/sec, 200mm/sec to 750mm/sec, and 200mm/sec to 500mm/sec.

60. A substrate at least partially coated with the coating composition according to any one of claims 1 to 24.

61. The substrate of claim 60 wherein the substrate comprises a vehicle substrate.

62. A substrate coated with a multilayer coating system, wherein the multilayer coating system comprises:

a first primer layer positioned over at least a portion of the substrate;

a second primer layer positioned over at least a portion of the first primer layer;

an optional clear coat layer positioned over at least a portion of the second primer layer; and

an optional top coat layer positioned over at least a portion of the clear coat layer and/or a portion of the second base coat layer;

wherein at least one of the first primer layer, the second primer layer, the clear coat layer, and the top coat layer comprises a coating obtained from the coating composition of any one of claims 1 to 24.

63. The substrate of claim 61 wherein the substrate comprises a vehicle substrate.

64. A substrate coated according to the method of any one of claims 25 to 45, wherein the coating is applied to a substantially vertical substrate.