Coated substrate

Abstract

A coated substrate comprises a coating extending over at least a portion of the substrate. The coating is obtainable from a coating composition comprising: (a) a polymeric binder; and (b) a feathering reducer comprising carboxylic acid-reactive functional groups. The coated portion of the substrate comprises a pretreatment layer. The pretreatment layer is obtainable from a pretreatment composition comprising a trivalent chromium compound. The present invention also extends to a method of coating the pretreated substrate and coated packaging, such as a metal can.

Description

Technical Field

[0001] The present invention relates to a coating composition. In particular, the present invention relates to a coating composition for food and / or beverage packaging. The present invention extends to articles coated with the coating composition and methods of preparing and applying the coating composition. Background Art

[0002] Coatings are used in a wide variety of applications. For example, many different coatings have been used to coat food and / or beverage packaging. Coating systems typically possess certain properties, such as the ability to be applied at high speeds, acceptable adhesion to substrates, food contact safety, and properties suitable for their end use. Typically, a coating will possess one or possibly two of these advantageous properties, depending on its ultimate end use. Summary of the Invention

[0003] According to the present invention, there is provided a coated substrate comprising a coating extending over at least a portion of the substrate, wherein the coating is obtainable from a coating composition comprising:

[0004] a. polymer binder; and

[0005] b. a feathering reducer comprising a carboxylic acid reactive functional group,

[0006] And wherein the coated portion of the substrate comprises a pretreatment layer, wherein the pretreatment layer is obtainable from a pretreatment composition comprising a trivalent chromium compound.

[0007] Also provided is a method of coating at least a portion of a substrate, the method comprising:

[0008] a. contacting the coating composition with a substrate, wherein the substrate comprises a pretreatment layer formed from a pretreatment composition comprising a trivalent chromium compound when the substrate is contacted with the coating composition on at least a portion of the substrate coated with the pretreatment layer;

[0009] b. allowing the coating composition to cure on the substrate to form a coating;

[0010] The coating composition comprises:

[0011] a. polymer binder; and

[0012] b. Feathering reducers comprising carboxylic acid reactive functional groups.

[0013] Also provided is a package at least partially coated with a coating composition comprising:

[0014] a. polymer binder; and

[0015] b. a feathering reducer comprising a carboxylic acid reactive functional group,

[0016] And wherein the coated portion of the substrate comprises a pretreatment layer, wherein the pretreatment layer is obtainable from a pretreatment composition comprising a trivalent chromium compound.

[0017] Also provided is a package, such as a metal can, at least partially coated on an end thereof with a coating composition comprising:

[0018] a. polymer binder; and

[0019] b. a feathering reducer comprising a carboxylic acid reactive functional group,

[0020] And wherein the coated portion of the substrate comprises a pretreatment layer, wherein the pretreatment layer is obtainable from a pretreatment composition comprising a trivalent chromium compound.

[0021] Also provided is a method of reducing feathering, the method comprising applying a pretreatment composition comprising a trivalent chromium compound to at least a portion of a substrate to form a pretreatment layer, and then applying to at least a portion of the substrate coated with the pretreatment layer a coating composition comprising:

[0022] a. polymer binder; and

[0023] b. a feathering reducer comprising a carboxylic acid reactive functional group,

[0024] to form a coating. DETAILED DESCRIPTION

[0025] When a can is opened, such as by using a pull tab, feathering occurs, and a portion of the film extends into the can opening. This can occur, for example, with beverage cans that have a pull tab or cans with full-mouth EOE. From a safety perspective, feathering is undesirable due to the potential for ingestion of the coating.

[0026] It has been found that this phenomenon is particularly pronounced in substrates that do not contain hexavalent chromium, such as in trivalent chromium pretreated substrates. Advantageously, it has been found that the use of the feathering reducing agent defined herein in the defined composition reduces feathering in packaging, such as on trivalent chromium pretreated substrates.

[0027] As used herein, a "feathering reducer" reduces feathering in a coating formed from a coating composition that includes the feathering reducer, compared to the same composition without the feathering reducer. 'Feathering' reported herein was measured by the following Test Protocol 1:

[0028] A trivalent chromium pretreated aluminum panel having a thickness of 0.21 mm was coated with the coating composition to obtain a film weight of 7.0 mg / in2 . The panels were then baked in a three-zone coil oven to a peak metal temperature of 240°C. The panels were then cut into 50.8mm by 88.9mm blocks, with the substrate particles extending perpendicular to the long length of the cut panels. The test panels were then inserted with the coated side facing up between the scoring tool and the anvil in a Carver press. The long edge of the panel rested against the guide block inside the press. The valve on the press base was tightened to clamp the panel into the Carver press. A force of 1500psi was applied to the hydraulic pressure gauge to form a score line simulating a pull ring. The depth of the score line was 0.18mm. Figure 1 Shown in FIG is a schematic diagram of a coated panel (100) including a score line simulating a pull ring (102). The simulated pull ring (102) extends perpendicular to the long length (I) of the panel. The end points (104, 106) of the score line (which together form the front of the simulated pull ring, i.e., the portion where the pull ring is first opened) are both arranged at the edge of the long length (I) of the panel. The dimensions of the simulated pull ring (102) are: A (48.0 mm); B (11.3 mm); C (24.0 mm); D (18.00 mm); E and F area (89.4 mm). 2 ); and G (10.6 mm). Length D extends from the upper endpoint of length C to the left and right vertices of circles E and F, respectively. Length G extends between the upper vertices of circles E and F. The panel is then removed from the tablet press and two spaced parallel cuts are made in the panel along the score line at the front end of the simulated pull ring. Each cut starts from the endpoint (104 and 106) of the score line and extends inward into the panel perpendicular to the long length. The cuts extend 6.4 mm into the panel along the corresponding portion of the score line and are spaced 11.3 mm apart. The panel is then completely immersed in deionized water at 250°F (121°C) for 30 minutes. The panel is then removed and immediately immersed in 22°C DI for 2 seconds. The panel is then removed from the deionized water. The cut portion of the simulated pull ring is bent 180° toward the coated surface of the panel. The panel is then inserted into a vise, where the panel is fixed along the long length and the edge extending from the score line is held in the vise. The cut portion of the simulated tab was then gripped with pliers and then pulled across the coated side of the panel 180° toward the opposite end of the tab at a rate of 1 second / cm. Feathering was then measured using a digital microscope. The length of the coating extending furthest into the tab opening was measured and recorded in mm.

[0029] The feathering reducer can reduce feathering in a coating formed from a coating composition including the feathering reducer by at least 20%, such as at least 30% or at least 40%, as measured by Test Protocol 1 above, compared to the same composition without the feathering reducer.

[0030] The feathering of a coating formed from the coating composition can be ≤ 0.8 mm, as measured by Test Protocol 1 above, such as ≤ 0.5 mm, ≤ 0.4 mm, or ≤ 0.35 mm.

[0031] When a portion of a coated substrate or package is separated from the remainder of the coated substrate or package, the feathering of the coated substrate or package may be ≤0.8 mm, such as ≤0.5 mm, ≤0.4 mm, or ≤0.35 mm, wherein the furthest length of the coating extending into the opening formed by separating the portion of the coated substrate or package is measured in mm using a digital microscope to record the feathering. The removable portion may be a portion of the coated substrate or package that is to be removed or separated from the remainder of the coated substrate or package during use, such as a pull ring on a beverage can.

[0032] The coated substrate or the package may have a wedge-shaped bend of ≤ 30 mm, such as ≤ 25 mm or ≤ 20 mm.

[0033] As reported herein, wedge bend was measured as follows. The coated panels were obtained by drawing the coating composition onto trivalent chromium pretreated NR6207 aluminum panels (AA5182 alloy) using a wire wound rod to obtain a dry coating weight of approximately 6.5 to 7.5 mg / square inch (msi). The coated panels were then immediately placed into a three-zone gas-fired conveyor oven for 10 seconds and baked to a peak metal temperature of 465°F (240.5°C). The coated panels were cut into 2 inch by 4 inch blocks with the substrate particles extending perpendicular to the long length of the cut panels. They were then bent along the long length of the panels on a 1 / 8 inch metal rod with the coated side facing outward. The bent coupons were then placed on a metal block into which wedges had been pre-cut, wherein the wedges had a taper of 0 to 1 / 8 inch along a 4 inch length. Once placed in the wedge, each bent coupon was struck with a 4-pound metal block from a height of 12 inches to form a wedge shape in which one end of the coated metal struck itself and a 1 / 8-inch space remained on the opposite end. The wedge-bent panels were then placed in an aqueous solution of copper sulfate and hydrochloric acid for one minute to intentionally etch the aluminum panels in areas where the coating failed and cracked. The etched wedge-bent panels were then examined with a microscope at 10x magnification to determine how far along the bend radius from the impact end the coating cracked. The flexibility results were reported as the length of the cracked area starting from the impact end.

[0034] The blush of the coated substrate or the packaging may be ≥4, such as ≥6 or ≥7.

[0035] As reported herein, blushing was measured as follows. The coated panels were obtained by stretching the coating composition onto trivalent chromium pretreated NR6207 aluminum panels (AA5182 alloy) using a wire wound rod to obtain a dry coating weight of approximately 6.5 to 7.5 mg / square inch (msi). The coated panels were then immediately placed into a three-zone gas-fired conveyor oven for 10 seconds and baked to a peak metal temperature of 465°F (240.5°C). The coated panels were then cut into 2-inch by 4-inch pieces, half immersed in deionized water, and then placed in a steam distiller at 250°F for 30 minutes. The panels were then cooled in deionized water, dried, and immediately rated for blushing and adhesion. Blushing was visually rated on a scale of 1-10, with a rating of "10" indicating no blushing and a rating of "0" indicating complete whitening of the film.

[0036] The adhesion of the coated substrate or the packaging may be ≥ 90, such as ≥ 95 or ≥ 99%.

[0037] Adhesion, as reported herein, was measured using Scotch 610 tape according to ASTM D 3359 Test Method B and rated on a scale of 0-100%, with "100%" indicating no adhesion failure and "0" indicating complete adhesion failure. Coated panels were obtained by stretching the coating composition onto trivalent chromium pretreated NR6207 aluminum panels (AA5182 alloy) using a wire-wound rod to obtain a dry coating weight of approximately 6.5 to 7.5 mg / square inch (msi). The coated panels were then immediately placed in a three-zone gas-fired conveyor oven for 10 seconds and baked to a peak metal temperature of 465°F (240.5°C).

[0038] The coating composition may include any suitable liquid carrier. The coating composition may include a single liquid carrier or a mixture of carriers. The liquid carrier may include water, an organic solvent, a mixture of water and an organic solvent, or a mixture of organic solvents.

[0039] The coating composition may be an aqueous coating composition. An aqueous coating composition may refer to a coating composition obtained by dissolving and / or dispersing a film-forming resin in an aqueous medium. An aqueous coating composition may include at least 10%, such as at least 30 wt % or at least 50 wt % of water, based on the total weight of the liquid carrier.

[0040] The coating composition may be an organic solvent-based coating composition. The organic solvent-based coating composition may be a coating composition comprising more than 90%, such as at least 95 wt % of an organic solvent based on the total weight of the liquid carrier.

[0041] The organic solvent may be sufficiently volatile to evaporate substantially completely from the coating composition during the curing process.

[0042] Suitable organic solvents include, but are not limited to, aliphatic hydrocarbons such as mineral spirits and high flash point naphtha; aromatic hydrocarbons such as benzene; toluene; xylene; solvent naphtha 100, 150, 200; organic solvents available from Exxon-Mobil Chemical Company under the trade name SOLVESSO (RTM); alcohols such as ethanol; n-propanol; isopropanol; isobutanol and n-butanol; ketones such as acetone; cyclohexanone; methyl isobutyl ketone; methyl ethyl ketone; esters such as ethyl acetate; butyl acetate; n-hexyl acetate; RHODIASOLV (RTM) RPDE (a blend of succinate and adipate esters commercially available from Solvay); glycols such as butanediol; glycol ethers such as methoxypropanol; ethylene glycol monomethyl ether; ethylene glycol monobutyl ether; dipropylene glycol methyl ether (Dowanol DPM), and combinations thereof.

[0043] The liquid carrier (when present) can be used in an amount of ≥5%, such as ≥10%, such as ≥20% or ≥30% or even ≥50% based on the total weight of the coating composition. The liquid carrier (when present) can be used in an amount of ≤90%, such as ≤80%, such as ≤75% or even ≤70% based on the total weight of the coating composition. The liquid carrier (when present) can be used in an amount of 5% to 90%, such as 10% to 80%, such as 20% to 75%, or even 30% to 70% based on the total weight of the coating composition. The liquid carrier (when present) can be used in an amount of 50 wt % to 70 wt % based on the total weight of the coating composition.

[0044] The polymeric binder may include a polyester binder material.

[0045] Polyester binder materials can include polyesters that can be obtained by polymerizing a polyacid component with a polyol component or by ring-opening polymerization, such as the ring-opening polymerization of a lactone component and / or an epoxy component. Polyester materials can include saturated polyesters. "Polyester materials," as used herein, include copolymers of polyacids and polyols, and also include modified polyesters, such as those modified by grafting another polymer onto the polyester. Examples of modified polyesters include acrylic modified polyester resins.

[0046] As used herein, "polyacid" and similar terms refer to compounds having two or more carboxylic acid groups, such as two (diacids), three (triacids), or four acid groups, and include polyacid esters (in which the acid groups are esterified) or anhydrides. The polyacid can be an organic polyacid.

[0047] The carboxylic acid groups of the polyacid may be linked by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; or an arylene group.

[0048] The polyester material may be formed from any suitable polyacid. Suitable examples of polyacids include, but are not limited to, maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanedioic acid; dodecanedioic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorendic anhydride; 1,3-cyclohexane dicarboxylic acid; 1,4-cyclohexane dicarboxylic acid; tricyclodecane polycarboxylic acid; endomethylene tetrahydrophthalic acid; endomethylene hexahydrophthalic acid; cyclohexane tetracarboxylic acid; cyclobutane tetracarboxylic acid; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all of the foregoing acids, and combinations thereof.

[0049] The polyacid component may include a diacid. Suitable examples of diacids include, but are not limited to, phthalic acid; isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic acid; hexahydrophthalic acid; maleic acid; succinic acid; itaconic acid; diester materials such as dimethyl ester derivatives, for example, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl fumarate, dimethyl orthophthalate, dimethyl succinate, dimethyl glutarate, dimethyl adipate; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the foregoing acids, and mixtures thereof.

[0050] The polyacid component may include: terephthalic acid (TPA), dimethyl terephthalate, isophthalic acid (IPA), dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, maleic anhydride, fumaric anhydride; and / or a monomer having an aliphatic group containing at least 15 carbon atoms.

[0051] The polyacid component may include terephthalic acid, isophthalic acid, dimethyl terephthalate, hexahydrophthalic anhydride, cyclohexane 1,4-dicarboxylic acid, maleic anhydride, and / or a monomer having an aliphatic group containing at least 15 carbon atoms.

[0052] The polyol component includes a polyol. As used herein, "polyol" and similar terms refer to a compound having two or more hydroxyl groups, such as two (diols), three (triols), or four hydroxyl groups (tetraols). The hydroxyl groups of the polyol can be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; or an arylene group. The polyol can be an organic polyol.

[0053] The polyester material may be formed from any suitable polyol. Examples of suitable polyols include, but are not limited to, the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycol, including 1,2-propylene glycol; 1,3-propylene glycol; butylethylpropylene glycol; 2-methyl-1,3-propylene glycol; and 2-ethyl-2-butyl-1,3-propylene glycol; butanediol, including 1,4-butanediol; 1,3-butanediol; and 2-ethyl-1,4-butanediol; pentanediol, including trimethylpentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediol, including 1,6-hexanediol; 2,2 ,4,4-tetraalkylcyclobutane-1,3-diol (TACD), such as 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD), caprolactone diols (e.g., the reaction product of a reaction mixture comprising ε-caprolactone and ethylene glycol); hydroxyalkylated bisphenols; polyether polyols, such as poly(oxytetramethylene) glycol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; trimethylolcyclohexane; bio-derived polyols, such as glycerol, sorbitol and isosorbide; monomers having an aliphatic group containing at least 15 carbon atoms, etc. or combinations thereof.

[0054] The diol may be selected from the following: ethylene glycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; but-2-ene-1,4-diol; 2,3-butanediol; 2-methyl-1,3-propanediol; 2,2'-dimethyl-1,3-propanediol (neopentyl glycol); 1,5-pentanediol; 3-methyl-1,5-pentanediol; 2,4-diethyl-1,5-pentanediol; 1,6-hexanediol; 2-ethyl-1,3-hexanediol; 2,2,4,4-Tetraalkylcyclobutane-1,3-diol (TACD), such as 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD), diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; isosorbide; 1,4-cyclohexanediol; and / or 1,1'-isopropylidene-bis(4-cyclohexanol); and mixtures thereof.

[0055] The polyol component may include: a polyol having at least three hydroxyl groups, such as trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; and / or a bio-derived polyol, such as glycerol and / or sorbitol. The polyol component having at least three hydroxyl groups may include: a triol or tetraol, such as trimethylolpropane; pentaerythritol; trimethylolethane; trimethylolbutane and / or glycerol. The polyol component having at least three hydroxyl groups may include: a triol, such as trimethylolpropane; trimethylolethane; and / or a trimethylolbutane, for example, trimethylolpropane.

[0056] The polyol having at least three hydroxyl groups may be present in an amount ≥ 0.1 wt%, such as ≥ 0.5 wt% or ≥ 0.7 wt%, for example ≥ 0.8 wt% or ≥ 0.9 wt%, such as ≥ 1 wt% as a proportion of the solid weight of the polyol component.

[0057] The polyol having at least three hydroxyl groups may be present in an amount ≤ 10 wt%, such as ≤ 8 wt% or ≤ 6 wt%, for example ≤ 5 wt% or ≤ 4 wt%, such as ≤ 3 wt% or ≤ 2 wt% as a proportion of the solid weight of the polyol component.

[0058] The polyol having at least three hydroxyl groups may be present in an amount of 0.1 wt % to 10 wt %, such as 0.5 wt % to 8 wt % or 0.7 wt % to 6 wt %, for example 0.8 wt % to 5 wt % or 0.9 wt % to 4 wt %, such as 1 wt % to 3 wt % or 1 wt % to 2 wt % as a proportion of the solid weight of the polyol component.

[0059] Specifically, the polyol component may include ethylene glycol (EG), 1,2-propylene glycol (PG), 2-methylpropylene glycol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), butylethylpropylene glycol (BEPD), trimethylolpropane (TMP) and / or 1,6-hexanediol.

[0060] Further details of such monomers having an aliphatic group containing at least 15 carbon atoms are disclosed in published PCT patent application WO 2018 / 111854, specifically, paragraphs

[016] to

[030] (inclusive). The entire contents of WO 2018 / 111854, and in particular paragraphs

[016] to

[030] (inclusive), are incorporated herein by reference in their entirety.

[0061] The polyacid component and / or the polyol component may include a sulfonated monomer. The sulfonated monomer may include a sulfonated diacid, such as a sulfonated aromatic diacid. The sulfonated monomer may include a salt thereof, such as an inorganic salt, for example a metal salt or an ammonium salt. Examples of metal salts include sodium salts, lithium salts, potassium salts, magnesium salts, calcium salts, iron salts, and the like.

[0062] The polyacid component may include a sulfonated monomer. Alternatively, the polyacid component may be substantially free of a sulfonated monomer.

[0063] The sulfonated monomer may include a metal salt of 5-(sulfo)-isophthalic acid, such as its sodium salt, which is known as 5-(sodium sulfonate)-isophthalic acid, also referred to herein as 5-SSIPA.

[0064] Sulfonated monomers may include: 5-(sodium sulfonate)-isophthalic acid, dimethyl 5-(sodium sulfonate)isophthalate, 5-(lithium sulfonate)isophthalic acid, and / or bis(2-hydroxyethyl)-5-(sodium sulfonate)isophthalate.

[0065] Wherein the sulfonated monomer is a polyacid, the sulfonated monomer may be present in an amount of 5 wt % to 20 wt % (eg, 7 wt % to 15 wt %) based on the solid weight of the polyacid component.

[0066] Wherein the sulfonated monomer is a polyol, the sulfonated monomer may be present in an amount of 5 wt % to 20 wt % (eg, 7 wt % to 15 wt %) based on the solid weight of the polyol component.

[0067] The polyester binder material may include an acrylic polyester resin, which may be a polyester resin having an acrylic polymer grafted thereon.

[0068] The acrylic polyester resin may be obtained by grafting an acrylic polymer and a polyester resin, wherein the polyester resin may be obtained by polymerizing:

[0069] i) a polyacid component, as defined above; and

[0070] ii) a polyol component, as defined above,

[0071] And wherein one of the polyacid component or the polyol component includes a functional monomer operable to impart functional groups to the polyester resin, such that an acrylic polymer can be grafted to the polyester resin by using the functional groups.

[0072] The polyacid component or polyol component of the polyester resin of the acrylic polyester resin includes a functional monomer operable to impart functional groups to the polyester resin. The functional groups are such that an acrylic polymer can be grafted onto the polyester resin using the functional groups. The functional groups may include ethylenically unsaturated carboxylic acid functional groups or epoxy functional groups. The functional groups may be present in the main chain of the polyester resin or in pendant chains derived therefrom.

[0073] The functional monomers may include ethylenically unsaturated monomers operable to impart ethylenically unsaturated functional groups to the backbone of the polyester resin or to side chains therefrom. The functional groups may include ethylenically unsaturated groups, which may be present in the backbone of the polyester resin.

[0074] Suitable functional monomers include maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, mesaconic acid, mesaconic anhydride, phenylmaleic acid, phenylmaleic anhydride, tert-butylmaleic acid, tert-butylmaleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methylmaleic acid, methylmaleic anhydride and / or trimethylolpropane monoallyl ether.

[0075] Where the functional monomer comprises a polyacid, the functional monomer may be present in an amount of 0.5 wt % to 10 wt %, such as 1 wt % to 5 wt %, based on the solid weight of the polyacid component.

[0076] Where the functional monomer comprises a polyol, the functional monomer may be present in an amount of 0.5 wt % to 10 wt %, such as 1 wt % to 5 wt %, based on the solid weight of the polyol component.

[0077] The functional monomer of the polyester resin of the acrylic polyester resin may include maleic acid, maleic anhydride and / or fumaric acid.

[0078] The polyester resin of the acrylic polyester resin can be modified with acrylic acid by grafting the acrylic modified polymer onto the polyester resin. Such grafting can occur by free radical polymerization, such as by free radical polymerization onto ethylenically unsaturated groups on the polyester material.

[0079] The acrylic modified polymer can be an acrylic monomer formed. The acrylic modified polymer can be grafted onto a polyester resin by polymerizing the acrylic monomer in the presence of a polyester material to form an acrylic polyester resin.

[0080] Various acrylic acid monomers can be combined to prepare acrylic acid-modified polymers. Examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid, dimethylaminoethyl methacrylate, butylaminoethyl (meth)acrylate, and / or HEMA phosphate (e.g., ethylene glycol methacrylate). Any other acrylic acid monomer known to those skilled in the art can also be used.

[0081] The term "(meth)acrylate" and similar terms are used conventionally and refer herein to both methacrylates and acrylates.

[0082] Suitable acrylic modified polymers are formed from monomers including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, cyclohexyl (meth)acrylate, allyl (meth)acrylate, dimethylaminoethyl methacrylate, butylaminoethyl (meth)acrylate, and / or HEMA phosphates (e.g., ethylene glycol methacrylate).

[0083] The acrylic monomers may include a ratio of methacrylate monomers to acrylate monomers of at least 1:1, such as at least 2:1, or at least 3:1, or at least 4:1, such as at least 5:1. The acrylic monomers may be substantially free of acrylate monomers. With respect to "methacrylate monomers" and "acrylate monomers," the ratio of these types of monomers in the acrylic monomers of the acrylic-modified polymer refers to the ratio of the total amount of methacrylate monomers to the total amount of acrylate monomers in all types of acrylic monomers forming the acrylic-modified polymer. For example, if the acrylic-modified polymer is formed from methyl methacrylate, methyl acrylate, and butyl acrylate, the ratio of the amount of methyl methacrylate to the combined amount of methyl acrylate and butyl acrylate will be at least 5:1.

[0084] The acrylic monomer may include a hydroxyl functional monomer such as hydroxyethyl (meth)acrylate. The hydroxyl functional monomer may be present in an amount of 5 wt % to 40 wt %, such as 5 wt % to 30 wt % or 10 wt % to 20 wt % based on the solid weight of the acrylic modified polymer.

[0085] The acrylic modified polymer may also include a certain amount (e.g., 0 wt % to 30 wt % based on the solid weight of the acrylic modified polymer) of non-acrylic monomers. Such non-acrylic monomers may include other ethylenically unsaturated monomers such as styrene, ethylene, propylene, vinyl toluene, butadiene, 1-octene or isoprene, vinyl esters (e.g., vinyl acetate) and / or nitriles (e.g., (meth)acrylonitrile).

[0086] It has been determined that the acrylic modified polymer may include methacrylic acid or acrylic acid to impart acid functionality to the acrylic modified polymer.The acid functionality on the acrylic modified polymer may be at least partially neutralized with a neutralizing agent.

[0087] The Tg of the acrylic modified polymer (which is a measure of the Tg of the acrylic modified polymer, polymerized as a simple acrylic polymer, rather than in the presence of (or grafted onto) a polyester resin) can be from 20° C. to 120° C. The Tg of the acrylic modified polymer can be calculated by the Fox equation as provided in “Coatings of Polymers and Plastics”, Ryntz RA and Yaneff PV, CRC Press, February 4, 2003, p. 134.

[0088] Suitable neutralizing agents contain ammonia or an amine functional moiety: methylethanolamine, dimethylethanolamine (DMEA), trimethylamine, diethylenetriamine.

[0089] The acid functional groups on the acrylic modified polymer can be at least 30% neutralized with a neutralizing agent. The acid functional groups on the acrylic modified polymer can be at least 50% neutralized with a neutralizing agent. The acid functional groups on the acrylic modified polymer can be at least 75% neutralized with a neutralizing agent.

[0090] The acrylic polyester resin may be formed from a polyester resin and an acrylic modified polymer in a weight ratio of 99 wt % to 50 wt % of the polyester resin to 50 wt % to 1 wt % of the acrylic modified polymer, such as a weight ratio of 95 wt % to 60 wt % of the polyester resin to 40 wt % to 5 wt % of the acrylic modified polymer, such as a weight ratio of 90 wt % to 65 wt % of the polyester resin to 35 wt % to 10 wt % of the acrylic modified polymer. For example, the acrylic polyester resin may be formed from a polyester resin and an acrylic modified polymer in a weight ratio of 85 wt % of the polyester resin to 15 wt % of the acrylic polymer.

[0091] The polyester binder material can be prepared in the presence of an esterification catalyst. The esterification catalyst can be selected to promote the esterification reaction and / or transesterification reaction of the components. Suitable examples of esterification catalysts for preparing high Mn polyesters include, but are not limited to, the following: metal compounds such as stannous octoate; stannous chloride; butyl stannous acid (hydroxybutyl tin oxide); monobutyltin tris(2-ethyl hexanoate); chlorobutyl stannous hydroxide; dibutyltin oxide; tetra-n-propyl titanate; tetra-n-butyl titanate; zinc acetate; acid compounds such as phosphoric acid; p-toluenesulfonic acid; dodecylbenzenesulfonic acid (DDBSA), tetraalkyl zirconium materials, antimony trioxide, germanium dioxide, bismuth octoate, and combinations thereof. The esterification catalyst can be dodecylbenzenesulfonic acid (DDBSA). The esterification catalyst can be dibutyltin oxide or stannous octoate.

[0092] The esterification catalyst, when present, may be used in an amount of 0.001% to 1% by weight of the total polymer component, such as 0.01% to 0.2%, such as 0.025% to 0.2% by weight of the total polymer component.

[0093] The polymeric binder may have any suitable number average molecular weight (Mn). The Mn of the polyester material may be ≥1,000 Daltons (Da=g / mole), such as ≥2,000 Da, such as ≥3,000 Da, or even ≥4,000 Da. The Mn of the polymeric binder may be ≤35,000 Da, such as ≤30,000 Da, such as ≤25,000 Da, or even ≤22,000 Da. The Mn of the polyester material may be from 1,000 Da to 35,000 Da, such as from 2,000 Da to 30,000 Da, such as from 3,000 Da to 25,000 Da, or even from 4,000 to 22,000 Da.

[0094] As reported herein, Mn and Mw are determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11 ("Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography", UV detector: 254 nm, solvent: labile THF, retention time marker: toluene, sample concentration: 2 mg / ml).

[0095] The polymer binder and / or the coating formed from the coating composition may have any suitable glass transition temperature (Tg). The Tg of the polymer binder and / or the coating formed from the coating composition may be ≥25°C and / or ≤200°C. The Tg of the polymer binder and / or the coating formed from the coating composition may be ≥25°C, or ≥30°C, or ≥35°C, such as ≥40°C or ≥45°C, or ≥50°C, such as ≥55°C or ≥60°C. The Tg of the polymer binder and / or the coating formed from the coating composition may be ≤200°C, such as ≤150°C, or ≤120°C, or ≤110°C, or ≤105°C. The Tg of the polymer binder and / or the coating formed from the coating composition may be from 25°C to 200°C, such as from 40°C to 150°C, such as from 50°C to 120°C, or from 50°C to 110°C, such as from 60°C to 105°C.

[0096] As reported herein, Tg is measured according to ASTM D6604-00(2013) (“Standard Practice for Glass Transition Temperatures of Hydrocarbon Resins by Differential Scanning Calorimetry,” heat flux differential scanning calorimetry (DSC), sample pan: aluminum, reference: blank, calibration: indium and mercury, sample weight: 10 mg, heating rate: 20°C / min).

[0097] The polymeric binder may have any suitable total hydroxyl value (OHV).The total OHV of the polyester material may be 0 to 120 mg KOH / g, such as 0 to 70 KOH / g, or 0 to 40 KOH / g, or 0 to 20 KOH / g or 0 to 15 KOH / g.

[0098] Suitably, the total OHV is expressed as solids.

[0099] As reported herein, the hydroxyl value is the number of mg of KOH equivalent to the hydroxyl groups in 1 g of material. A solid polymer binder sample (0.13 g) was accurately weighed into an Erlenmeyer flask and dissolved in 20 ml of tetrahydrofuran using appropriate slight heating and stirring. 10 ml of a solution of 0.1 M 4-(dimethylamino)pyridine in tetrahydrofuran (catalyst solution) and 5 ml of a solution of 9 vol% acetic anhydride in tetrahydrofuran (i.e., 90 ml of acetic anhydride in 910 ml of tetrahydrofuran; acetylation solution) were then added to the mixture. After 5 minutes, 10 ml of an 80 vol% tetrahydrofuran solution (i.e., 4 parts by volume of tetrahydrofuran to 1 part of distilled water; hydrolysis solution) was added. After 15 minutes, 10 ml of tetrahydrofuran was added and the solution was titrated with 0.5 M ethanolic potassium hydroxide (KOH). A blank sample test was also performed in which the solid polyester sample was omitted. The resulting hydroxyl number was calculated in mg KOH / g using the following equation:

[0100]

[0101] Where V1 is the titer of the polymer binder sample in KOH solution (ml) and V2 is the titer of the blank sample in KOH solution (ml).All values ​​reported herein for total hydroxyl value were measured in this way.

[0102] The polymeric binder may have any suitable acid value (AV). The polyester material may have an AV of ≥3 KOH / g, such as ≥6 KOH / g or ≥9 KOH / g. The polymeric binder may have an AV of ≤50 KOH / g, such as ≤40 KOH / g or ≤30 KOH / g, or ≤25 KOH / g. The polymeric binder may have an AV of 0 to 50 KOH / g, such as 3 to 40 KOH / g, or 6 to 30 KOH / g, or 9 to 25 KOH / g.

[0103] Suitably, AV is represented by a solid.

[0104] As reported herein, AN is determined by titration with 0.1 M methanolic potassium hydroxide (KOH) solution. A solid polymer binder sample (0.1 g) is accurately weighed into an Erlenmeyer flask and dissolved in 25 ml of dimethylformamide containing phenolphthalein indicator using appropriate gentle heating and stirring. The solution is then allowed to cool to room temperature and titrated with 0.1 M methanolic potassium hydroxide solution. The resulting acid number is expressed in mg KOH / g and calculated using the following equation:

[0105] Acid value = titer of KOH solution (ml) × molar concentration of KOH solution (M) × 56.1

[0106] Solid sample weight (g)

[0107] All values ​​reported herein for acid number are measured in this manner.

[0108] The composition may comprise ≥40%, such as ≥50% or ≥60% by weight of the total solids weight of the composition of the polymer binder. The composition may comprise ≤99.9%, such as ≤99.5%, or 99%, or ≤98%, or ≤97% or ≤96% by weight of the total solids weight of the composition of the polymer binder. The composition may comprise from 40% to 99.9%, such as from 50% to 98%, or from 60% to 96% by weight of the total solids weight of the composition of the polymer binder.

[0109] The feathering reducing agent includes a carboxylic acid reactive functional group. As used herein, a carboxylic acid reactive functional group can be a group that is operable to react with a carboxylic acid group during curing of the coating composition on the substrate, for example to form a new covalent bond connecting the residue of the carboxylic acid reactive functional group to the residue of the carboxylic acid group.

[0110] The feathering reducer may include a functional group selected from the group consisting of hydroxyl, epoxide, acid functionality, amine, amide, imine, nitrile, phosphated epoxy, and / or oxazole.

[0111] Feathering reducing agents may be selected from:

[0112] i. an acrylic feathering reducer comprising a functional group selected from the group consisting of: hydroxyl, epoxide, phosphated epoxide and / or acid functional groups;

[0113] ii. Hydroxyl functional polyester feathering reducer;

[0114] iii. a feathering reducing agent comprising a functional group selected from the group consisting of amines, amides, imides and / or nitriles;

[0115] iv. Phosphated epoxy resin feathering reducer;

[0116] v. Phenolic resin feathering reducer; and / or

[0117] vi. Feathering reducers comprising oxazolyl functional groups.

[0118] The coating composition may include an acrylic feathering reducer (i) comprising functional groups selected from the group consisting of hydroxyl, epoxide, phosphated epoxide, and / or acid functional groups.

[0119] The acrylic feathering reducer (i) may be in the form of an acrylic (co)polymer formed from monomers comprising an acrylic monomer such as a (hetero)aliphatic (alkyl)acrylate or (alkyl)acrylic acid, optionally together with another vinyl monomer (such as another acrylic monomer). Suitable acrylic monomers include, but are not limited to, alkyl (alkyl)acrylates, such as C1 to C6 alkyl)acrylates, for example, C1 to C6 alkyl (meth)acrylates and (alkyl)acrylic acids such as (C1 to C6 alkyl)acrylic acid. The acrylic monomers may include functional groups.

[0120] The acrylic monomer may be selected from the following: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; propyl (meth)acrylate; butyl (meth)acrylate; cyclohexyl (meth)acrylate; benzyl methacrylate; 2-ethylhexyl (meth)acrylate; isobornyl (meth)acrylate; lauryl (meth)acrylate; hydroxyl-functional acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and / or phosphates thereof such as ethylene glycol methacrylate; and / or glycidyl-functional acrylates such as glycidyl (meth)acrylate.

[0121] As used herein, the terms "(alk)acrylate," "(meth)acrylate," and similar terms are conventionally used herein to refer to both alkacrylates and acrylates, such as methacrylates and acrylates.

[0122] Other vinyl monomers may be selected from: (meth)acrylonitrile; vinyl ethers, such as vinyl butyl ether; styrene, vinyl toluene, propylene, 1-octene, vinyl esters, such as vinyl acetate, vinyl pyrrolidone and / or vinyl pyridine.

[0123] Acrylic (co)polymers can be formed from monomers including compatible crosslinking monomers, such as allyl (meth)acrylate, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol di(meth)acrylate, 1,4-butylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol dimethacrylate and 1,6-hexanediol diacrylate, especially compatible acrylic crosslinking monomers.

[0124] For the avoidance of doubt, acrylic acid in the context of the present invention includes materials formed from monomers including acrylic acid monomers (as defined herein). Acrylic acid can include any suitable amount of acrylic acid monomers. For example, based on the total solid weight of the monomers forming acrylic acid, acrylic acid can include at least 10wt%, such as at least 20wt%, such as at least 30wt%, such as at least 40wt%, such as at least 50wt%, such as at least 60wt%, such as at least 70wt%, such as at least 80wt% or even at least 90wt% of acrylic acid monomers. Based on the total solid weight of the monomers forming acrylic acid, acrylic acid can include up to 100wt% of acrylic acid monomers.

[0125] The acrylic acid may include 10 wt % to 100 wt % of acrylic acid monomers based on the total solid weight of acrylic acid-forming monomers.

[0126] For example, acrylic acid can include up to 90 wt% of additional ethylenically unsaturated monomers, based on the total solid weight of the monomers that form acrylic acid. Acrylic acid can include up to 80 wt%, such as up to 70 wt%, such as up to 60 wt%, such as up to 50 wt%, such as up to 40 wt%, such as up to 30 wt%, such as up to 20 wt%, or even up to 10 wt% of additional ethylenically unsaturated monomers, based on the total solid weight of the monomers that form acrylic acid. Acrylic acid can include no additional ethylenically unsaturated acrylic acid monomers, i.e., 0 wt%, based on the total solid weight of the monomers that form acrylic acid.

[0127] The acrylic feathering reducer may be substantially free, substantially free, or completely free of monomers comprising epoxy groups. With respect to monomers comprising epoxy groups, substantially free means that the acrylic acid is formed from monomers comprising less than 5 wt% of monomers comprising epoxy groups, based on the total weight of the monomers forming the acrylic acid. With respect to monomers comprising epoxy groups, substantially free means that the acrylic acid is formed from monomers comprising less than 1 wt% of monomers comprising epoxy groups, based on the total weight of the monomers forming the acrylic acid. With respect to monomers comprising epoxy groups, completely free means that the acrylic acid is formed from monomers comprising less than 0.01 wt% of monomers comprising epoxy groups, based on the total weight of the monomers forming the acrylic acid. The acrylic acid may be formed from monomers excluding monomers comprising epoxy groups (i.e., 0 wt%), based on the total weight of the monomers forming the acrylic acid.

[0128] The acrylic feathering reducer may be completely free of monomers comprising epoxy groups.

[0129] The acrylic feathering reducer may be substantially free, substantially free, or completely free of glycidyl methacrylate. With respect to glycidyl methacrylate, substantially free means that the acrylic acid is formed from monomers that include less than 5 wt% of glycidyl methacrylate, based on the total weight of the monomers from which the acrylic acid is formed. With respect to glycidyl methacrylate, substantially free means that the acrylic acid is formed from monomers that include less than 1 wt% of glycidyl methacrylate, based on the total weight of the monomers from which the acrylic acid is formed. With respect to glycidyl methacrylate, completely free means that the acrylic acid is formed from monomers that include less than 0.01 wt% of glycidyl methacrylate, based on the total weight of the monomers from which the acrylic acid is formed. The acrylic acid may be formed from monomers that do not include glycidyl methacrylate (i.e., 0 wt%), based on the total weight of the monomers from which the acrylic acid is formed.

[0130] The acrylic feathering reducer may be completely free of glycidyl methacrylate.

[0131] The acrylic feathering reducer may be substantially free, substantially free, or completely free of styrene. With respect to styrene, substantially free means that the acrylic acid is formed from monomers that include less than 5 wt% styrene, based on the total weight of the monomers from which the acrylic acid is formed. With respect to styrene, substantially free means that the acrylic acid is formed from monomers that include less than 1 wt% styrene, based on the total weight of the monomers from which the acrylic acid is formed. With respect to styrene, completely free means that the acrylic acid is formed from monomers that include less than 0.01 wt% styrene, based on the total weight of the monomers from which the acrylic acid is formed. The acrylic acid may be formed from monomers that do not include styrene (i.e., 0 wt%), based on the total weight of the monomers from which the acrylic acid is formed.

[0132] Acrylic feather reducers can be completely styrene-free.

[0133] The acrylic feathering reducer can be formed by any suitable method. Acrylic acid can be formed by solution polymerization or emulsion polymerization.

[0134] Acrylic feathering reducers can be formed by solution polymerization. Suitable solution polymerization methods are well known to those skilled in the art. A solution polymerization method can include a variety of components, which can be referred to as a solution polymerization reaction mixture.

[0135] The solution polymerization reaction mixture may include a solution polymerization monomer component. The solution polymerization monomer component may include an acrylic acid monomer as described above. The solution polymerization monomer component may optionally include additional ethylenically unsaturated monomers as described above.

[0136] The solution polymerization reaction mixture may further include an initiator. The initiator may be a free radical initiator. Suitable initiators include, but are not limited to, tert-butyl perbenzoate; tert-butyl peroxy-3,5,5-trimethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; di-tert-butyl peroxide; tert-butyl peracetate; tert-butyl peroxyoctanoate; azo-type initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); persulfate initiators such as ammonium persulfate, sodium persulfate or potassium persulfate and combinations thereof. The initiator may be soluble in the solution polymerization reaction mixture. The initiator may be soluble in the monomer mixture.

[0137] The initiator may include t-butyl peroxyoctoate, t-butyl perbenzoate, or a combination thereof.

[0138] The solution polymerization reaction mixture may include a solvent or a mixture of solvents. Suitable solvents are well known to those skilled in the art. Examples of suitable solvents include, but are not limited to, alcohols such as n-butanol, pentanol, or hexanol; glycols such as butanediol; glycol ethers such as 2-butoxyethanol, 1-methoxypropan-2-ol, or dipropylene glycol monomethyl ether; and combinations thereof. The solvent may include a mixture of solvents. Those skilled in the art will appreciate that the solvent or mixture of solvents is typically selected such that the monomer mixture is substantially soluble in the solvent or mixture of solvents.

[0139] The solution polymerization monomer components are polymerized in a solvent or a mixture of solvents.The solution polymerization of the solution polymerization monomer components is typically carried out as a free radical initiated solution polymerization in a solvent or a mixture of solvents.

[0140] Solution polymerization is typically carried out in a suitable reaction vessel. The solution polymerization monomer components, initiator and / or solvent or solvent mixture can be added to the reaction vessel in any suitable order. For example, the solvent or solvent mixture can be added to the reaction vessel before the solution polymerization monomer components and / or initiator are added to the reaction vessel. The solution polymerization monomer components and initiator can be added to the reaction vessel at the same time. The solution polymerization monomer components and / or initiator can be added to the reaction vessel within any suitable time period.

[0141] The solution polymerization can be carried out at any suitable temperature. The solution polymerization can be carried out at an elevated temperature. The solution polymerization can be carried out at a temperature of 80°C to 200°C, such as 100°C to 180°C, such as 120°C to 160°C, such as 130°C to 150°C, or even 135°C to 140°C. The solution polymerization can be carried out under reflux.

[0142] Acrylic feathering reducers can be formed by emulsion polymerization. Suitable emulsion polymerization methods are well known to those skilled in the art. Emulsion polymerization methods can include a variety of components, which can be referred to as an emulsion polymerization reaction mixture.

[0143] The emulsion polymerization reaction mixture may include an emulsion polymerization monomer component. The emulsion polymerization monomer component may include an acrylic monomer as described above. The emulsion polymerization monomer component may optionally include additional ethylenically unsaturated monomers as described above.

[0144] The emulsion polymerization reaction mixture may further include an initiator. Suitable initiators are as described above for solution polymerization.

[0145] The emulsion polymerization reaction mixture may include water.

[0146] The monomer components of the emulsion polymerization reaction mixture are polymerized in water. The polymerization of the monomer components of the emulsion polymerization reaction mixture is usually carried out as a free radical initiated aqueous emulsion polymerization. The monomer components of the emulsion polymerization reaction mixture can form an oil phase in water.

[0147] The emulsion polymerization reaction mixture may include a buffer. Suitable buffers are well known to those skilled in the art. The buffer may be operable to act as a hydrogen ion acceptor. Examples of suitable buffers include, but are not limited to, sodium bicarbonate.

[0148] The emulsion polymerization reaction mixture may include a surfactant. The surfactant may be an anionic, cationic, or nonionic stabilizer. Suitable examples of anionic surfactants include, but are not limited to, alkyl sulfates, such as sodium lauryl sulfate or sodium polyoxyethylene alkyl ether sulfate; aryl sulfonates, such as sodium dodecylbenzenesulfonate; sulfosuccinates, such as sodium diisobutylsulfosuccinate, sodium dioctylsulfosuccinate, and sodium dicyclohexylsulfosuccinate; and combinations thereof. Suitable examples of nonionic emulsifiers include, but are not limited to, fatty alcohol ethoxylates, such as polyethylene glycol monolauryl ether; fatty acid ethoxylates, such as polyethylene glycol monostearate or polyethylene glycol monolaurate; polyether block polymers, such as polyethylene glycol / polypropylene glycol block polymers, also known as pluronics, typical commercial products of this type include Tergitol (RTM) XJ, XH, or XD commercially available from Dow Chemical; and combinations thereof. Suitable examples of cationic emulsifiers include, but are not limited to: amine salts, for example, cetyltrimethylammonium chloride or benzyldodecyldimethylammonium bromide; and combinations thereof. Those skilled in the art will appreciate that mixtures of anionic and cationic emulsifiers are generally not desirable.

[0149] The surfactant can be polymerized. The surfactant can be polymerized with the acrylic acid in the emulsion polymerization. For example, the surfactant can be polymerized with the monomers that form the acrylic acid in the emulsion polymerization.

[0150] However, the emulsion polymerization reaction mixture may be substantially free, substantially free, or completely free of surfactant. Substantially free with respect to surfactant means that the emulsion polymerization reaction mixture includes less than 5 wt% of surfactant, based on the total weight of the emulsion polymerization reaction mixture. Substantially free with respect to surfactant means that the emulsion polymerization reaction mixture includes less than 1 wt% of surfactant, based on the total weight of the emulsion polymerization reaction mixture. Completely free with respect to surfactant means that the emulsion polymerization reaction mixture includes less than 0.01 wt% of surfactant, based on the total weight of the emulsion polymerization reaction mixture. The emulsion polymerization reaction mixture may include no (i.e., 0 wt%) surfactant.

[0151] Emulsion polymerization is typically carried out in a suitable reaction vessel. The emulsion polymerization monomer components, initiator, and / or water of the emulsion polymerization reaction mixture can be added to the reaction vessel in any suitable order. For example, water can be added to the reaction vessel before the emulsion polymerization monomer components and / or initiator are added to the reaction vessel. The initiator can be added to the reaction vessel before the emulsion polymerization monomer components. The emulsion polymerization monomer components and / or initiator can be added to the reaction vessel over any suitable time period.

[0152] The emulsion polymerization can be carried out at any suitable temperature. The emulsion polymerization can be carried out at a temperature of 20°C to 150°C, such as 40°C to 120°C, such as 50°C to 100°C, such as 60°C to 95°C, such as 70°C to 90°C, or even at 80°C. The temperature is generally kept constant throughout the emulsion polymerization process.

[0153] Emulsion polymerized acrylic acid can be in a core / shell arrangement.

[0154] The shell can be formed from a variety of components, which can be referred to as a shell mixture. The shell mixture can include acrylic monomers as described above. The emulsion polymerization reaction mixture can optionally include additional ethylenically unsaturated monomers as described herein.

[0155] The shell mixture may further comprise an initiator. Suitable initiators are as described above for solution polymerization.

[0156] The shell mixture is typically polymerized to form the shell polymer. Polymerization of the shell mixture is typically performed as a free radical initiated solution polymerization in a solvent or a mixture of solvents. Solvents that can be used for this process include, but are not limited to, alcohols such as n-butanol, pentanol, or hexanol; or glycol ethers such as 2-butoxyethanol, 1-methoxypropan-2-ol, or dipropylene glycol monomethyl ether. Polymerization can be performed at elevated temperatures. Polymerization can be performed in the range of 80°C to 150°C. Polymerization can be efficiently performed by adding the shell mixture to the solvent mixture over a set period of time. The shell mixture can be polymerized to form the shell polymer prior to contact with the components of the core mixture.

[0157] Where the shell mixture includes an α,β-ethylenically unsaturated carboxylic acid, the shell polymer will have pendant carboxylic acid functional groups. This may be referred to as a carboxylic acid functional shell polymer.

[0158] The carboxylic acid functional shell polymer can be contacted with a base to form a water-dispersible salt. The carboxylic acid functional groups in the carboxylic acid functional shell polymer can be at least partially neutralized with a base. Typically, at least 10% of the available carboxylic acid groups are neutralized. Essentially all of the available carboxylic acid groups can be neutralized with a base. The base used for this neutralization can include an amine-functional material, or a mixture of amine-functional materials. Suitable examples of amine-functional materials include ammonia, triethylamine, diethylamine, trimethylamine, and morpholine or hydroxylamine materials, such as ethanolamine, N-methylethanolamine, and N,N-dimethylethanolamine.

[0159] The shell polymer can be dispersed in an aqueous medium. In this way, an aqueous dispersion or solution of the shell polymer can be formed.

[0160] The shell mixture may be polymerized to form the shell polymer by emulsion polymerization in an aqueous medium, thereby forming an aqueous dispersion or solution of the shell polymer.

[0161] The core may be formed from a variety of components, which may be referred to as a core mixture. The core mixture may include acrylic monomers as described above. The emulsion polymerization reaction mixture may optionally include additional ethylenically unsaturated monomers as described herein.

[0162] The polymer formed from the shell mixture, for example an aqueous dispersion thereof, can serve as a dispersant for a subsequent polymerization, which can be of a mixture of α,β-ethylenically unsaturated monomers, such as the core mixture.

[0163] The core mixture may further include an initiator. Suitable initiators are as described above for solution polymerized acrylic acid.

[0164] The core mixture can be polymerized at a temperature in the range of 30°C to 99°C, such as in the range of 50°C to 95°C, such as in the range of 80°C to 90°C. The polymerization of the core mixture can occur in the presence of the polymer formed by the polymerization of the shell mixture, typically by emulsion polymerization, to form a core / shell polymer. Typical polymerizations can be performed by adding the core mixture to an aqueous dispersion of the shell polymer at a controlled rate over a period of time. During the polymerization, the mixture can be mixed, such as by stirring, and the temperature can be kept approximately constant.

[0165] Other methods of polymerizing the core mixture include, but are not limited to, mixing all or part of the core ethylenically unsaturated material with an aqueous dispersion of the shell polymer and then adding the remaining core components, including the initiator, to the resulting mixture over a set period of time. Suitable temperatures for this type of process are generally in the range of 50°C to 95°C.

[0166] For core / shell compositions, the ratio of core mixture (monomer and initiator) to shell mixture (monomer and initiator) can be 20:80 to 90:10 by weight, such as 60:40 to 80:20, or even 70:30 to 75:25 by weight.

[0167] The acrylic feathering reducer may have an Mn of at least 500 Da, such as at least 1,000 Da, such as at least 1,500 Da, such as at least 2,000 Da, or even at least 2,500 Da. The acrylic acid may have an Mn of at most 250,000 Da, such as at most 200,000 Da, such as at most 150,000 Da, such as at most 100,000 Da, such as at most 50,000 Da, such as at most 25,000 Da, or even at most 20,000 Da. The Mn of acrylic acid can be 500 to 250,000 Daltons (Da = g / mole), such as 1,000 Da to 200,000 Da, such as 1,000 Da to 100,000 Da, such as 1,500 Da to 50,000 Da, such as 2,000 Da to 25,000 Da, or even 2,500 Da to 20,000 Da.

[0168] The acrylic feathering reducer may have a Mw of at least 500 Da, such as at least 1,000 Da, such as at least 1,500 Da, such as at least 2,000 Da, such as at least 2,500 Da, such as at least 5,000 Da, such as at least 6,000 Da, or even at least 7,000 Da. The acrylic acid may have a Mw of at most 500,000 Da, such as at most 250,000 Da, such as at most 200,000 Da, such as at most 150,000 Da, such as at most 100,000 Da, such as at most 75,000 Da, or even at most 50,000 Da. The Mw of acrylic acid can be 500 to 500,000 Daltons (Da = g / mole), such as 1,000 Da to 250,000 Da, such as 2,000 Da to 200,000 Da, such as 2,500 Da to 150,000 Da, such as 5,000 Da to 100,000 Da, such as 6,000 Da to 75,000 Da or even 7,000 Da to 50,000 Da.

[0169] The acrylic feathering reducer may have a Tg of at least -50°C, such as at least -25°C, such as at least 0°C, such as at least 5°C, such as at least 10°C, or even at least 15°C. The acrylic acid may have a Tg of at most 250°C, such as at most 200°C, such as at most 150°C, such as at most 125°C, such as at most 100°C, or even at most 75°C. The acrylic acid may have a Tg of from -50°C to 250°C, such as from -25°C to 200°C, such as from 0°C to 150°C, such as from 5°C to 125°C, such as from 10°C to 100°C, or even from 15°C to 80°C.

[0170] The acrylic (co)polymer may be formed from monomers including glycidyl functional acrylate monomers.The acrylic (co)polymer may be formed from monomers including glycidyl functional acrylate monomers and hydroxyl functional monomers.

[0171] Acrylic (co)polymers may be formed from monomers including methyl methacrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and / or glycidyl methacrylate (GMA).

[0172] The coating composition may include an acrylic feathering reducer (i) formed from monomers including a glycidyl functional acrylate and methyl methacrylate, butyl methacrylate, butyl acrylate, and / or hydroxyethyl methacrylate.

[0173] The coating composition may include an acrylic feathering reducer (i) formed from monomers including a glycidyl functional acrylate and a butyl methacrylate, such as isobutyl methacrylate, ethylhexyl acrylate, and / or 4-hydroxybutyl acrylate.

[0174] The acrylic feathering reducer (i) may include hydroxyl and epoxy groups.

[0175] The acrylic feather reducing agent (i), such as the acrylic feather reducing agent (i) containing hydroxyl and epoxy groups, can be formed from monomers comprising ≥10 wt %, such as ≥15 wt % or ≥20 wt % of a hydroxyl functional monomer, based on the total weight of the monomers. The acrylic feather reducing agent (i) can be formed from monomers comprising ≤80 wt %, such as ≤60 wt % or ≥40 wt % of a hydroxyl functional monomer, based on the total weight of the monomers. The acrylic feather reducing agent (i) can be formed from 10% to 80%, such as 15 wt % to 60 wt % or 20 wt % to 40 wt % of a hydroxyl functional monomer, based on the total weight of the monomers.

[0176] Acrylic feathering reducers (i), such as acrylic feathering reducers (i) containing hydroxyl and epoxy groups, can be formed from monomers comprising ≥ 25 wt %, such as ≥ 40 wt % or ≥ 50 wt % of a glycidyl functional monomer (e.g., glycidyl methacrylate), based on the total weight of the monomers. Acrylic feathering reducers (i) can be formed from monomers comprising ≤ 90 wt %, such as ≤ 80 wt % or ≥ 70 wt % of a glycidyl functional monomer, based on the total weight of the monomers. Acrylic feathering reducers (i) can be formed from monomers comprising 25% to 90 wt %, such as 40 wt % to 80 wt % or 50 wt % to 70 wt % of a glycidyl functional monomer, based on the total weight of the monomers.

[0177] The composition may include a phosphorylated epoxy resin acrylic feathering reducer (i). As used herein with respect to the phosphorylated epoxy resin acrylic feathering reducer (i), the term "phosphorylated epoxy resin" refers to a compound that includes the reaction product of a reaction mixture that includes an epoxy functional acrylic and a phosphoric acid source, a phosphonic acid source, or a combination thereof.

[0178] The epoxy functional acrylic may be as defined above. The epoxy functional acrylic may have an epoxy equivalent weight ≥ 1,000, such as ≥ 2,000 or ≥ 2,500.

[0179] As reported herein, epoxy resin equivalent is the mass of a sample containing one mole of unreacted epoxide functional groups in grams. A phosphorylated epoxy resin sample (5.0 g) is accurately weighed into a 120 ml beaker and 1.5 g of tetraethylammonium bromide is added. A magnetic stirring bar is placed in a beaker and 40 mL of dichloromethane and 20 mL of acetic acid are added. The beaker is securely covered and stirred until the sample is completely dissolved. The sample solution is placed in the titration position and titrated potentiometrically with 0.1 N perchloric acid titrant. A blank solution containing all of the above reagents except the sample is also run.

[0180] The epoxide content of the sample is equal to:

[0181]

[0182] Where T is the titer of the perchloric acid solution of the sample, in mL.

[0183] R is the titer used for the blank in mL, N = equivalents of perchloric acid titrant, and 1000 = grams to milligrams conversion factor.

[0184] All values ​​of EEW of phosphated epoxy resins were determined using the method described above.

[0185] Epoxy functional acrylics can be formed from monomers including glycidyl functional acrylate monomers and hydroxyl functional monomers.

[0186] The epoxy-functional acrylic can be formed from monomers comprising ≥ 20%, such as ≥ 30% or ≥ 35% by weight of a hydroxyl-functional monomer, based on the total weight of the monomers. The epoxy-functional acrylic can be formed from monomers comprising ≥ 2%, such as ≥ 4% or ≥ 6% by weight of a glycidyl-functional acrylate monomer, based on the total weight of the monomers. The epoxy-functional acrylic can be formed from monomers comprising ≤ 30%, such as ≥ 20% or ≥ 10% by weight of a glycidyl-functional acrylate monomer, based on the total weight of the monomers.

[0187] Epoxy functional acrylics can be formed from monomers including glycidyl functional acrylate monomers, hydroxyl functional monomers, and cyclic group-containing monomers, such as aromatic group-containing monomers.

[0188] The epoxy-functional acrylic can be formed from monomers including > 20%, such as > 30 wt% or > 35 wt% of a cyclic group-containing monomer, based on the total weight of the monomers.

[0189] Epoxy functional acrylics can be formed from monomers including glycidyl functional acrylates and styrene and / or hydroxyethyl methacrylate.

[0190] The phosphoric acid source can include phosphoric acid, such as orthophosphoric acid, for example, 100% orthophosphoric acid or an aqueous solution of phosphoric acid. The aqueous solution of phosphoric acid can include water containing 70% to 90% by weight of phosphoric acid, such as water containing 85% by weight of phosphoric acid. Other forms of phosphoric acid can be used, such as superphosphoric acid, diphosphoric acid and triphosphoric acid as the phosphoric acid source. Similarly, a polymeric anhydride or partial anhydride of phosphoric acid can be used as the phosphoric acid source. The phosphonic acid source can include an organic phosphonic acid. The organic phosphonic acid can include 3-aminopropylphosphonic acid, 4-methoxyphenylphosphonic acid, benzylphosphonic acid, butylphosphonic acid, carboxyethylphosphonic acid, diphenylphosphinic acid, dodecylphosphonic acid, ethylenediphosphonic acid, heptadecanylphosphonic acid, methylbenzylphosphinic acid, naphthylmethylphosphinic acid, octadecylphosphonic acid, pentylphosphonic acid, methylphenylphosphinic acid, phenylphosphonic acid, styrenephosphonic acid, dodecylbis-1,12-phosphonic acid and / or poly(ethylene glycol)phosphonic acid.

[0191] The reactants may include ≥ 80%, such as ≥ 90 wt% or ≥ 95 wt% of the epoxy functional acrylic based on the combined weight of the phosphoric acid source and the epoxy functional acrylic.

[0192] The reactants may include ≥0.5%, such as ≥1 wt % or ≥1.5 wt % of a phosphoric acid source and / or a phosphonic acid source, based on the combined weight of the phosphoric acid source and the polyepoxide. The reactants may include ≤15%, such as ≤10 wt % or ≤5 wt % of a phosphoric acid source and / or a phosphonic acid source, based on the combined weight of the phosphoric acid source and the polyepoxide.

[0193] By "acid functional" it is meant that the acid functional acrylic feathering reducer includes pendant acid groups, such as pendant carboxylic acid groups. The pendant acid groups can be terminal groups or can be on the backbone of the acid functional acrylic. The acid functional acrylic feathering reducer can include carboxyl groups.

[0194] The acid functional acrylic feather reducing agent (i) can be formed from monomers including > 10%, such as > 20 wt% or > 25 wt% of an acid functional monomer, based on the total weight of the monomers.

[0195] The acid functional monomer may include an (alkyl) acrylic acid, such as a (C1 to C6 alkyl) acrylic acid. The acid functional monomer may include an alkyl acrylic acid and an acrylic acid, such as methacrylic acid and acrylic acid.

[0196] The acid-functional acrylic feathering reducer (i) can be formed from monomers comprising ≥2% alkyl acrylic monomer and ≥10% acrylic monomer, such as ≥5 wt% alkyl acrylic monomer and ≥15 wt% acrylic monomer or ≥7 wt% alkyl acrylic monomer and ≥20 wt% acrylic monomer, based on the total weight of the monomers.

[0197] The acid functional acrylic feathering reducing agent may have an acid value of at least 10 mg KOH / g, such as at least 25 mg KOH / g, such as at least 50 mg KOH / g, such as at least 75 mg KOH / g, such as at least 100 mg KOH / g, such as at least 125 mg KOH / g, such as at least 150 mg KOH / g, such as at least 175 mg KOH / g, such as at least 200 mg KOH / g. The acid functional acrylic feathering reducing agent may have an acid value of at most 500 mg KOH / g, such as at most 475 mg KOH / g, such as at most 450 mg KOH / g, such as at most 425 mg KOH / g, such as at most 400 mg KOH / g, such as at most 375 mg KOH / g, such as at most 350 mg KOH / g, such as at most 325 mg KOH / g, such as at most 300 mg KOH / g, or even at most 250 mg KOH / g. The acid functional acrylic feathering reducer may have an acid value of 10 to 500 mg KOH / g, such as 25 to 475 mg KOH / g, such as 50 to 450 mg KOH / g, such as 75 to 425 mg KOH / g, such as 100 to 400 mg KOH / g, such as 125 to 375 mg KOH / g, such as 150 to 350 mg KOH / g, such as 175 to 325 mg KOH / g, such as 200 to 300 mg KOH / g.

[0198] The coating composition may include an acrylic feathering reducer (i) in an amount of ≥0.1%, such as ≥0.5% or ≥1% by weight of the solids of the coating composition. The coating composition may include an acrylic feathering reducer (i) in an amount of ≤40%, such as ≤20% or ≤15% by weight of the solids of the coating composition. The coating composition may include an acrylic feathering reducer (i) in an amount of 0.1% to 40%, such as 0.5% to 20% or 1% to 15% by weight of the solids of the coating composition.

[0199] The coating composition may include an amount of epoxide functional acrylic feathering reducer (i) of ≥0.1%, such as ≥0.5 wt% or ≥1 wt%, based on the weight of the solids of the coating composition. The coating composition may include an amount of epoxide functional acrylic feathering reducer (i) of ≤20%, such as ≤15 wt%, or ≤10 wt%, or ≤7 wt%, or ≤5 wt%, based on the weight of the solids of the coating composition. The coating composition may include an amount of epoxide functional acrylic feathering reducer (i) of 0.1% to 20%, such as 0.5 wt% to 15 wt%, or 0.5 wt% to 10 wt%, or 1 wt% to 7 wt%, or 1 wt% to 5 wt%, based on the weight of the solids of the coating composition.

[0200] The coating composition may include the phosphorylated epoxy resin acrylate feathering reducer and / or the acid functional acrylic feathering reducer (i) in an amount of ≥1%, such as ≥4 wt%, such as ≥6 wt%, based on the total solid weight of the coating composition. The coating composition may include the phosphorylated epoxy resin acrylate feathering reducer and / or the acid functional acrylic feathering reducer (i) in an amount of ≤40%, such as ≤20 wt% or ≤15 wt%, based on the total solid weight of the coating composition. The coating composition may include the phosphorylated epoxy resin acrylate feathering reducer and / or the acid functional acrylic feathering reducer (i) in an amount of 1% to 40%, such as 4 wt% to 20 wt% or 5 wt% to 15 wt%, based on the total solid weight of the coating composition.

[0201] The hydroxyl-functional polyester feathering reducer (ii) may include polyesters obtainable by polymerizing a polyacid component with a polyol component or by ring-opening polymerization, such as ring-opening polymerization of a lactone component and / or an epoxy component.

[0202] Suitable examples of polyacids include, but are not limited to, maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanedioic acid; dodecanedioic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorendic anhydride; 1,3-cyclohexane dicarboxylic acid; 1,4-cyclohexane dicarboxylic acid; tricyclodecane polycarboxylic acid; endomethylene tetrahydrophthalic acid; endomethylene hexahydrophthalic acid; cyclohexane tetracarboxylic acid; cyclobutane tetracarboxylic acid; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all of the foregoing acids, and combinations thereof.

[0203] Suitable examples of diacids include, but are not limited to, the following: phthalic acid; isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic acid; hexahydrophthalic acid; maleic acid; succinic acid; itaconic acid; diester materials, such as dimethyl ester derivatives, for example, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl fumarate, dimethyl orthophthalate, dimethyl succinate, dimethyl glutarate, dimethyl adipate; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all of the foregoing acids; and mixtures thereof.

[0204] The polyacid component may include: terephthalic acid (TPA), dimethyl terephthalate, isophthalic acid (IPA), dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, maleic anhydride, fumaric anhydride; and / or a monomer having an aliphatic group containing at least 15 carbon atoms.

[0205] The polyacid component may include isophthalic acid, dimethyl terephthalate, hexahydrophthalic anhydride, cyclohexane 1,4-dicarboxylic acid, and / or a monomer having an aliphatic group containing at least 15 carbon atoms.

[0206] Suitable examples of polyols include, but are not limited to, the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycol, including 1,2-propylene glycol; 1,3-propylene glycol; butylethylpropylene glycol; 2-methyl-1,3-propylene glycol; and 2-ethyl-2-butyl-1,3-propylene glycol; butanediol, including 1,4-butanediol; 1,3-butanediol; and 2-ethyl-1,4-butanediol; pentanediol, including trimethylpentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediol, including 1,6-hexanediol; 2,2, 4,4-tetraalkylcyclobutane-1,3-diol (TACD), such as 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD), caprolactone diols (e.g., the reaction product of a reaction mixture comprising ε-caprolactone and ethylene glycol); hydroxyalkylated bisphenols; polyether polyols, such as poly(oxytetramethylene) glycol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; trimethylolcyclohexane; bioderived polyols, such as glycerol, sorbitol, and isosorbide; monomers having an aliphatic group containing at least 15 carbon atoms, etc., or combinations thereof.

[0207] The diol may be selected from the following: ethylene glycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; but-2-ene-1,4-diol; 2,3-butanediol; 2-methyl-1,3-propanediol; 2,2'-dimethyl-1,3-propanediol (neopentyl glycol); 1,5-pentanediol; 3-methyl-1,5-pentanediol; 2,4-diethyl-1,5-pentanediol; 1,6-hexanediol; 2-ethyl-1,3-hexanediol; 2,2,4,4-Tetraalkylcyclobutane-1,3-diol (TACD), such as 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD), diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; isosorbide; 1,4-cyclohexanediol; and / or 1,1'-isopropylidene-bis(4-cyclohexanol); and mixtures thereof.

[0208] The polyol component may include: a polyol having at least three hydroxyl groups, such as trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; and / or a bio-derived polyol, such as glycerol and / or sorbitol. The polyol component having at least three hydroxyl groups may include: a triol or tetraol, such as trimethylolpropane; pentaerythritol; trimethylolethane; trimethylolbutane and / or glycerol. The polyol component having at least three hydroxyl groups may include: a triol, such as trimethylolpropane; trimethylolethane; and / or a trimethylolbutane, for example, trimethylolpropane.

[0209] The polyol having at least three hydroxyl groups may be present in an amount ≥ 0.1 wt%, such as ≥ 0.5 wt% or ≥ 0.7 wt%, for example ≥ 0.8 wt% or ≥ 0.9 wt%, such as ≥ 1 wt% as a proportion of the solid weight of the polyol component.

[0210] The polyol having at least three hydroxyl groups may be present in an amount ≤ 10 wt%, such as ≤ 8 wt% or ≤ 6 wt%, for example ≤ 5 wt% or ≤ 4 wt%, such as ≤ 3 wt% or ≤ 2 wt% as a proportion of the solid weight of the polyol component.

[0211] The polyol having at least three hydroxyl groups may be present in an amount of 0.1 wt % to 10 wt %, such as 0.5 wt % to 8 wt % or 0.7 wt % to 6 wt %, for example 0.8 wt % to 5 wt % or 0.9 wt % to 4 wt %, such as 1 wt % to 3 wt % or 1 wt % to 2 wt % as a proportion of the solid weight of the polyol component.

[0212] Specifically, the polyol component may include ethylene glycol (EG), 1,2-propylene glycol (PG), 2-methylpropylene glycol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), butylethylpropylene glycol (BEPD), trimethylolpropane (TMP) and / or 1,6-hexanediol.

[0213] Further details of such monomers having an aliphatic group containing at least 15 carbon atoms are disclosed in published PCT patent application WO 2018 / 111854, specifically, paragraphs

[016] to

[030] (inclusive). The entire contents of WO 2018 / 111854, and in particular paragraphs

[016] to

[030] (inclusive), are incorporated herein by reference in their entirety.

[0214] The total hydroxyl value (OHV) of the hydroxyl functional polyester feathering reductant (ii) may be ≥65 mg KOH / g, such as ≥70 mg KOH / g or ≥80 mg KOH / g, or such as ≥90 mg KOH / g or ≥100 mg KOH / g.

[0215] The coating composition may include the hydroxyl-functional polyester feathering reducing agent (ii) in an amount of ≥0.1%, such as ≥1 wt%, or ≥2 wt%, or ≥3 wt%, based on the weight of the solids of the coating composition. The coating composition may include the hydroxyl-functional polyester feathering reducing agent (ii) in an amount of ≤40%, such as ≤20 wt%, or ≤15 wt%, or ≤10 wt%, based on the weight of the solids of the coating composition. The coating composition may include the hydroxyl-functional polyester feathering reducing agent (ii) in an amount of 0.1% to 40%, such as 1 wt% to 20 wt%, or 2 wt% to 15 wt%, or 3 wt% to 10 wt%, based on the weight of the solids of the coating composition.

[0216] The feathering reducer (iii) may include a combination of at least two different types of groups selected from amine, amide, imine, nitrile and / or hydroxyl groups. The feathering reducer (iii) may include an amine group as well as an amide group, an imine group, a nitrile group and / or a hydroxyl group.

[0217] The feathering reducer (iii) may include at least two amine groups, such as at least two primary amine groups and / or secondary amine groups, such as at least two primary amine groups.

[0218] The feathering reducing agent (iii) can be a small molecule. As used herein, "small molecule" with respect to the feathering reducing agent (iii) can mean a feathering reducing agent (iii) having a molecular weight of ≤1,500 Daltons (Da), such as ≤1,200 Da or ≤1,000 Da. Suitable examples of small molecule feathering reducing agents (iii) include, but are not limited to, dicyandiamide (DICY), 2,4,6-tris(dimethylaminomethyl)phenol (TAP) and / or hydroxyalkylamides and derivatives thereof.

[0219] The feathering reducer (iii) may be a polymer, such as a polyamide. The polyamide feathering reducer may include an amine terminated polyamide.

[0220] The polyamide feathering reducing agent (iii) may have an amine value of ≥150 mg KOH / gram resin, such as ≥180 mg KOH / gram resin, or ≥200 mg KOH / gram resin, or ≥220 mg KOH / gram resin.

[0221] As reported herein, the amine number is determined by titration with 0.1 M perchloric acid (HClO 4 ) in glacial acetic acid solution. A solid polyamide sample (0.1 g) is accurately weighed into an Erlenmeyer flask and dissolved in 25 ml of acetic acid containing methyl violet as an indicator using appropriate gentle heating and stirring. The solution is then allowed to cool to room temperature and titrated with 0.1 M glacial acetic acid solution containing perchloric acid. The resulting amine number is expressed in mg KOH / g and is calculated using the following equation:

[0222] Amine number = titer of HClO4 solution (ml) × molar concentration of HClO4 solution (M) × 56.1

[0223] Solid sample weight (g)

[0224] All values ​​reported herein for amine number are measured in this manner.

[0225] The coating composition may include a feathering reducer (iii) in an amount of ≥0.001 wt%, such as ≥0.01 wt% or ≥0.05 wt%, based on the weight of the solids of the coating composition. The coating composition may include a feathering reducer (iii) in an amount of ≤5 wt%, such as ≤3 wt%, or ≤2 wt%, or ≤1 wt%, based on the weight of the solids of the coating composition. The coating composition may include a feathering reducer (iii) in an amount of 0.001% to 5%, such as 0.01 wt% to 3 wt%, or 0.01 wt% to 2 wt%, or 0.05 wt% to 1 wt%, based on the weight of the solids of the coating composition.

[0226] The composition may include a phosphorylated epoxy resin feathering reducer (iv). As used herein with respect to feathering reducer (iv), the term "phosphorylated epoxy resin" refers to a compound comprising the reaction product of a reaction mixture comprising a polyepoxide and a phosphoric acid source, a phosphonic acid source, or a combination thereof.

[0227] Polyepoxides can include any compound or mixture of compounds having more than 1.0 epoxy group per molecule. Polyepoxides can include polyglycidyl ethers of polyols, such as cyclic polyols in which the bridging group includes a cyclic moiety, for example, polyphenols or alicyclic polyols, such as the diglycidyl ether of bisphenol A, bisphenol F, or 1,4-cyclohexanedimethanol. Polyols can include any compound or mixture of compounds having more than 1.0 hydroxyl group per molecule. Polyols can include diols.

[0228] As will be appreciated, such polyepoxides can be prepared by etherification of polyphenols with epichlorohydrin in the presence of a base. Suitable polyphenols that can be used to produce polyepoxides include, but are not limited to: 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)isobutane; 2,2-bis(4-hydroxytert-butylphenyl)propane; bis(2-hydroxynaphthyl)methane; 1,5-dihydroxynaphthalene; 1,1-bis(4-hydroxy-3-allylphenyl)ethane; and 4,4-bis(4'-hydroxyphenyl)valeric acid.

[0229] The phosphoric acid source can include phosphoric acid, such as orthophosphoric acid, for example, 100% orthophosphoric acid or an aqueous solution of phosphoric acid. The aqueous solution of phosphoric acid can include water containing 70% to 90% by weight of phosphoric acid, such as water containing 85% by weight of phosphoric acid. Other forms of phosphoric acid can be used, such as superphosphoric acid, diphosphoric acid and triphosphoric acid as the phosphoric acid source. Similarly, a polymeric anhydride or partial anhydride of phosphoric acid can be used as the phosphoric acid source. The phosphonic acid source can include an organic phosphonic acid. The organic phosphonic acid can include 3-aminopropylphosphonic acid, 4-methoxyphenylphosphonic acid, benzylphosphonic acid, butylphosphonic acid, carboxyethylphosphonic acid, diphenylphosphinic acid, dodecylphosphonic acid, ethylenediphosphonic acid, heptadecanylphosphonic acid, methylbenzylphosphinic acid, naphthylmethylphosphinic acid, octadecylphosphonic acid, pentylphosphonic acid, methylphenylphosphinic acid, phenylphosphonic acid, styrenephosphonic acid, dodecylbis-1,12-phosphonic acid and / or poly(ethylene glycol)phosphonic acid.

[0230] The reactants may comprise ≥70%, such as ≥80% or ≥82% by weight of the polyepoxide, based on the combined weight of the phosphoric acid source and the polyepoxide. The reactants may comprise ≤95%, such as ≤90% or ≤88% by weight of the polyepoxide, based on the combined weight of the phosphoric acid source and the polyepoxide. The reactants may comprise from 70% to 95%, such as from 80% to 90% or from 82% to 88% by weight of the polyepoxide, based on the combined weight of the phosphoric acid source and the polyepoxide.

[0231] The reactants may include ≥5% by weight of the phosphoric acid source and the polyepoxide, such as ≥10% by weight or ≥12% by weight of the phosphoric acid source and / or the phosphonic acid source. The reactants may include ≤30% by weight of the phosphoric acid source and the polyepoxide, such as ≤20% by weight or ≤18% by weight of the phosphoric acid source and / or the phosphonic acid source. The reactants may include 5% to 30% by weight of the phosphoric acid source and the polyepoxide, such as 10% to 20% by weight or 12% to 18% by weight of the phosphoric acid source and / or the phosphonic acid source.

[0232] The coating composition may include a feathering reducer (iv) in an amount of ≥0.1%, such as ≥0.5% or ≥1% by weight of the solids of the coating composition. The coating composition may include a feathering reducer (iv) in an amount of ≤40%, such as ≤20% by weight, or ≤15% by weight, or ≤10% by weight of the solids of the coating composition. The coating composition may include a feathering reducer (iv) in an amount of 0.1% to 40%, such as 0.5% to 20% by weight, or 0.5% to 15% by weight, or 1% to 10% by weight of the solids of the coating composition.

[0233] The phenolic feathering reducing agent (v) may have an aliphatic hydroxyl equivalent weight on the solid of ≥60, such as ≥80 or ≥90. The aliphatic hydroxyl equivalent weight of the phenolic feathering reducing agent (v) may be ≤500, such as ≤300, or ≤200 or ≤160. The aliphatic hydroxyl equivalent weight of the phenolic feathering reducing agent (v) may be from 60 to 500 or from 60 to 300, such as from 80 to 200 or from 90 to 160.

[0234] As reported herein, aliphatic hydroxyl equivalent weight is determined by the following equation:

[0235] Molecular mass of the structure / number of aliphatic hydroxyl functional groups in the structure

[0236] For polymer structures, the structural masses and functional groups used are average values. This can also be derived by taking a weighted average of the equivalent weights of idealized structures according to routine practice by those skilled in the art.

[0237] The phenolic feathering reducer (v) may include a resin that is a reaction product of a reaction mixture including phenol or a derivative thereof and an aldehyde, such as formaldehyde.

[0238] The phenolic feather reducing agent (v) may be substantially non-alkylated / non-etherified.

[0239] Non-limiting examples of phenol or its derivative reactants that can be used to form the phenolic feather reducing agent (v) are phenol, butylphenol, xylenol and / or cresols (o-cresol, m-cresol and / or p-cresol). The phenol or its derivative reactants can include phenol and cresol. The phenol or its derivative reactants can include ≥80% phenol based on the combined weight of all phenol or its derivative reactants.

[0240] The phenolic feathering reducing agent (v) may be of the resol type. "Resol type" means a resin formed in the presence of an alkaline (base) catalyst and optionally an excess of formaldehyde.

[0241] The phenolic feathering reducing agent (v) may be water miscible.

[0242] The coating composition may include a phenolic feathering reducer (v) in an amount of ≥0.1%, such as ≥0.3% or ≥0.5% by weight, based on the weight of the solids of the coating composition. The coating composition may include a phenolic feathering reducer (v) in an amount of ≤40%, such as ≤20%, or ≤15%, or ≤10% by weight, based on the weight of the solids of the coating composition. The coating composition may include a phenolic feathering reducer (v) in an amount of 0.1% to 40%, such as 0.3% to 20%, or 0.5% to 15%, or 0.5% to 10% by weight, based on the weight of the solids of the coating composition.

[0243] The general preparation of phenolic resins is described in "The Chemistry and Application of Phenolic Resins or Phenoplasts", edited by Dr. Oldring, Volume V, Part I; John Wiley and Sons / Cita Technology Limited, London, 1997.

[0244] Advantageously, it has been found that phenolic feathering reducers (v) can improve feathering and can also maintain or improve other desirable properties such as hairing, mobility, stability and / or foaming.

[0245] The pH of the feathering reducer (vi) comprising an oxazolyl functional group may be from 7 to 11, such as from 7.5 to 10.5 or from 8 to 10.

[0246] The oxazoline value of the feathering reducing agent (vi) comprising an oxazolyl functional group may be ≥2 mmol / g, such as ≥3 mmol / g or ≥4 mmol / g. The oxazoline value of the feathering reducing agent (vi) comprising an oxazolyl functional group may be ≤15 mmol / g, such as ≤10 mmol / g or ≤8 mmol / g. The oxazoline value of the feathering reducing agent (vi) comprising an oxazolyl functional group may be from 2 to 15 mmol / g, such as from 3 to 10 mmol / g or from 4 to 8 mmol / g.

[0247] The feathering reducing agent (vi) comprising an oxazolyl functional group may be a (co)polymer comprising an oxazolyl functional group.

[0248] The Tg of the feathering reducer (vi) comprising an oxazolyl functional group may be ≥30° C., such as ≥40° C. or ≥45° C. The Tg of the feathering reducer (vi) comprising an oxazolyl functional group may be ≤120° C., such as ≤100° C. or ≤70° C. The Tg of the feathering reducer (vi) comprising an oxazolyl functional group may be from 30° C. to 120° C., such as from 40° C. to 100° C. or from 45° C. to 70° C.

[0249] The feathering reducer (vi) comprising an oxazolyl functional group may have an Mn of ≥10,000 Da, such as ≥15,000 Da or ≥17,000 Da. The feathering reducer (vi) comprising an oxazolyl functional group may have an Mn of ≤100,000 Da, such as ≤50,000 Da or ≤30,000 Da. The feathering reducer (vi) comprising an oxazolyl functional group may have an Mn of 10,000 to 100,000 Da, such as 15,000 to 50,000 Da or 17,000 to 30,000 Da.

[0250] The feathering reducing agent (vi) comprising an oxazolyl functional group may have an Mw of ≥10,000 Da, such as ≥40,000 Da or ≥60,000 Da. The feathering reducing agent (vi) comprising an oxazolyl functional group may have an Mw of ≤200,000 Da, such as ≤100,000 Da or ≤80,000 Da. The feathering reducing agent (vi) comprising an oxazolyl functional group may have an Mw of 10,000 to 200,000 Da, such as 40,000 to 100,000 Da or 60,000 to 80,000 Da.

[0251] The feathering reducer (vi) comprising oxazolyl functional groups can be polyoxazoline.The further details comprising the suitable polyoxazoline of oxazolyl functional groups are disclosed in U.S. Patent Application 2019 / 0185706, the full content of which is incorporated herein by reference in its entirety. Specifically with reference to paragraphs

[0026] to

[0049] of U.S. Patent Application 2019 / 0185706, the content of which is incorporated herein by reference in its entirety. The further details comprising the suitable polyoxazoline of oxazolyl functional groups are also disclosed in patent application WO 2019 / 116327, the full content of which is incorporated herein by reference in its entirety. Specifically with reference to paragraphs

[0043] to

[0051] of patent application WO 2019 / 116327, the content of which is incorporated herein by reference in its entirety. Further details of suitable polyoxazolines including oxazolyl functional groups are also disclosed in patent application WO 2019 / 116328, the entire contents of which are incorporated herein by reference in their entirety. With particular reference to paragraphs

[0020] to

[0023] of patent application WO 2019 / 116328, the contents of which are incorporated herein by reference in their entirety.

[0252] The feathering reducer (vi) comprising an oxazolyl functional group may be an acrylic feathering reducer comprising an oxazolyl functional group. The acrylic feathering reducer (vi) comprising an oxazolyl functional group may be an acrylic as defined above with respect to the acrylic feathering reducer (i).

[0253] The coating composition may include the feathering reducing agent (vi) comprising an oxazolyl functional group in an amount of ≥1 wt %, such as ≥2 wt % or ≥3 wt %, based on the weight of the solids of the coating composition. The coating composition may include the feathering reducing agent (vi) comprising an oxazolyl functional group in an amount of ≤40 wt %, such as ≤20 wt %, or ≤15 wt % or ≤10 wt %, based on the weight of the solids of the coating composition. The coating composition may include the feathering reducing agent (vi) comprising an oxazolyl functional group in an amount of 1% to 40%, such as 1 wt % to 20 wt %, or 2 wt % to 15 wt % or 3 wt % to 10 wt %, based on the weight of the solids of the coating composition.

[0254] Examples of suitable feathering reducers include: DOMACRYL 285 (available from Helios Resins); TEGO LP1600, TEGO DS1300, TEGO LP1611 (available from Evonik Industries); DOMOPOL 5144 (available from Helios resins); Versamid 115 (available from Gabriel); Curaphen 40-804 (available from Bitrez); and Epocros WS500, Epocros WS300, and Epocros WS700 (available from Nippon Shokubai).

[0255] The coating composition may include an epoxy resin. When the composition includes a feathering reducer comprising a functional group selected from amine, amide, imine and / or nitrile, the coating composition may include an epoxy resin. The coating composition may include a small molecule feathering reducer (iii) and an epoxy resin.

[0256] The coating composition may include a polyester additive. The polyester additive may include the reaction product of a reaction mixture comprising (i) a polyacid, (ii) a polyol, and (iii) phosphoric acid, such as the reaction product of a reaction mixture comprising a precursor polyester and phosphoric acid (e.g., phosphoric acid). The Mn of the polyester may be 2000 to 10,000. The hydroxyl number of the polyester may be 20 to 75. The acid value of the polyester may be 15 to 25.

[0257] The polyester additive may comprise a solution of a copolymer with acidic groups having an acid value of 15 mg KOH / g up to 100 mg KOH / g. Examples of commercially available suitable acidic polyesters include BYK-4510 (available from Byk Altana) or PLUSOLIT H-PD (available from commercially available) or BORCHI GEN HMP-F or BORCHI GEN HE (commercially available from OMG Borchers).

[0258] The acidic polyester may generally comprise the reaction product of a reaction mixture comprising:

[0259] (a) a polyester having an Mn of 2000 to 10,000, a hydroxyl number of 20 to 75, and an acid number of 15 to 25; said polyester being a condensation polymer of:

[0260] (i) a polyol component, such as a mixture comprising diols and triols,

[0261] (ii) a polyacid component, such as α,β ethylenically unsaturated polyformic acid,

[0262] as well as

[0263] (b) Phosphoric acid.

[0264] The polyester additive can be added in an amount of 0.1 wt % to 15 wt % (based on the solid weight of the coating composition), such as 2 wt % to 12 wt % (based on the solid weight of the coating composition). The polyester additive can be present in an amount of 4 wt % to 10 wt % (based on the solid weight of the coating composition).

[0265] Further suitable examples of polyester additives are given in WO 2012 / 162301, the contents of which are incorporated herein by reference in their entirety.

[0266] The coating composition can be substantially free or completely free of polyester additives, including the reaction product of a reaction mixture comprising (i) a polyacid, (ii) a polyol, and (iii) phosphoric acid, such as the reaction product of a reaction mixture comprising a precursor polyester and phosphoric acid. Substantially free with respect to polyester additives means that the coating composition comprises less than 0.05 wt% of polyester additives, based on the total solids weight of the coating composition. Completely free with respect to polyester additives means that the coating composition comprises less than 0.01 wt% of polyester additives, based on the total solids weight of the coating composition. The coating composition can include no polyester additives, i.e., 0 wt% based on the total solids weight of the coating composition.

[0267] The coating composition may include a cross-linking material. The coating composition may include any suitable cross-linking material. Suitable cross-linking materials are well known to those skilled in the art.

[0268] The cross-linking material may be operable to cross-link a polyester material. The cross-linking material may be a monomolecule, a dimer, an oligomer, a (co)polymer, or a mixture thereof. The cross-linking material may be a dimer or a trimer.

[0269] Suitable cross-linking materials include, but are not limited to, phenolic resins (phenol-formaldehyde resins); aminoplast resins (or triazine-formaldehyde resins); amino resins; epoxy resins; isocyanate resins; β-hydroxy(alkyl)amide resins; alkylated urethane resins; polyacids; anhydrides; organometallic acid-functional materials; polyamines; and / or polyamides and combinations thereof.

[0270] Suitable examples of phenolic resins are those formed by reacting phenol with an aldehyde or ketone, such as by reacting phenol with an aldehyde, such as by reacting phenol with formaldehyde or acetaldehyde, or even by reacting phenol with formaldehyde. Non-limiting examples of phenols that can be used to form phenolic resins are phenol, butylbenzene powder, xylenol, and cresol. The general preparation of phenolic resins is described in "The Chemistry and Application of Phenolic Resins or Phenoplasts," edited by Dr. Oldring, Volume V, Part I; John Wiley and Sons / Cita Technology Limited, London, 1997. The phenolic resin can be a resol type. "Resol type" refers to a resin formed in the presence of an alkaline (base) catalyst and optionally an excess of formaldehyde. Suitable examples of commercially available phenolic resins include, but are not limited to, those sold under the trade name PHENODUR (RTM), such as PHENODUR EK-827, PHENODUR VPR1785, PHENODUR PR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODUR PR612, or PHENODUR PH2024, commercially available from Allnex; resins sold under the trade name BAKELITE (RTM), such as BAKELITE 6582LB, BAKELITE 6535, BAKELITE PF9989, or BAKELITE PF6581, commercially available from Sumitomo Bakelite Co., Ltd.; SFC commercially available from SI Group; 112; DUREZ (RTM) 33356 commercially available from SHHPP Corporation (SHHPP); ARALINK (RTM) 40-852 commercially available from Bidli Corporation; or a combination thereof.

[0271] Suitable examples of isocyanate resins include, but are not limited to, the following: isophorone diisocyanate (IPDI), such as those sold under the trade name DESMODUR (RTM), for example DESMODUR VP-LS2078 / 2 or DESMODUR PL 340, commercially available from Cevstro, or those sold under the trade name VESTANANT (RTM), for example VESTANANT B 1370, VESTANANT B 118 6A, or VESTANANT B 1358A, commercially available from Evonik; blocked aliphatic polyisocyanates based on hexamethylene diisocyanate (HDI), such as those sold under the trade name DESMODUR (RTM), for example DESMODUR BL3370 or DESMODUR BL3175SN, commercially available from Covestro; and polyisocyanates commercially available from Asahi Kasei Corporation. those sold under the trade name DURANATE (RTM) commercially available from KASEI, such as DURANATE MF-K60X; those sold under the trade name TOLONATE (RTM) commercially available from Vencorex Chemicals, such as TOLONATE D2, or those sold under the trade name TRIXENE (RTM) commercially available from Baxenden, such as TRIXENE-BI-7984 or TRIXENE 7981; or combinations thereof.

[0272] The cross-linking material may contain nitrogen. The cross-linking material may be in the form of an amine or amide material. The cross-linking material may include an amine or amide material substituted with a hydroxyl group.

[0273] The cross-linking material may include a hydroxyalkylamide material, such as a beta-hydroxyalkylamide material.

[0274] Crosslinking materials may include commercially available beta-hydroxyalkylamide crosslinks, for example, PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N',N'-tetrakis(2-hydroxypropyl)adipamide.

[0275] The cross-linking material may be in the form of a urea material. The cross-linking material may include a hydroxyl-substituted urea material. The cross-linking material may include a hydroxyl-functional alkyl polyurea material.

[0276] The hydroxyl functional alkyl polyurea material may include a material according to formula (I):

[0277]

[0278] wherein R comprises an isocyanurate moiety, a biuret moiety, an allophanate moiety, a glycoluril moiety, a benzoguanamine moiety, a polyetheramine moiety, and / or a polymeric moiety other than a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently hydrogen, an alkyl group having carbon atoms, or a hydroxy-functional alkyl group having 2 or more carbon atoms, and at least one R1 is a hydroxy-functional alkyl group having 2 or more carbon atoms; and n is 2 to 6.

[0279] The hydroxyl functional alkyl polyurea material may include a material according to formula (II):

[0280]

[0281] wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, an isocyanurate moiety, a biuret moiety, an allophanate moiety, a glycoluril moiety, a benzoguanamine moiety, a polyetheramine moiety, and / or a polymeric moiety other than a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently hydrogen, an alkyl group having carbon atoms, or a hydroxy-functional alkyl group having 2 or more carbon atoms, and at least one R1 is a hydroxy-functional alkyl group having 2 or more carbon atoms; and n is 2 to 6.

[0282] Further details of suitable hydroxyl-functional alkyl polyurea materials are disclosed in PCT patent application WO 2017 / 123955, the entire contents of which are incorporated herein by reference.

[0283] Suitable examples of aminoplast resins include aminoplast resins that are reaction products of a reaction mixture comprising a triazine such as melamine or benzoguanamine and formaldehyde. These concentrates can typically be etherified with methanol, ethanol, butanol, or a mixture thereof. For the chemistry, preparation, and use of aminoplast resins, see "The Chemistry and Applications of Amino Crosslinking Agents or Aminoplasts," Vol. V, Part 11, p. 21 ff., Dr. Oldring, ed.; John Wiley & Sons / Cita Technology Limited, London, 1998. Suitable examples of commercially available aminoplast resins include, but are not limited to, those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL MF980 (commercially available from Ineos); those sold under the trade name CYMEL (registered trademark), such as CYMEL 303 and CYMEL 1128 (available from Allnex Industries); and combinations thereof.

[0284] The cross-linking material may include a material according to formula (III)

[0285]

[0286] Wherein R1 represents hydrogen, alkyl (such as C1 to C 20 Alkyl), aryl (such as C4 to C 24 Aryl), aralkyl (such as C5 to C 25 Aralkyl) or -NR6R7;

[0287] R2 to R7 each independently represent hydrogen, alkyl (such as C1 to C 20 Alkyl), aryl (such as C4 to C 24 Aryl), aralkyl (such as C5 to C 25 Aralkyl) or -CHR8OR9;

[0288] wherein R8 and R9 each independently represent hydrogen, an alkyl group (such as C1 to C 20 Alkyl), aryl (such as C4 to C 24 Aryl), aralkyl (such as C5 to C 25 Aralkyl), alkoxyalkyl (such as C2 to C 40 Alkoxyalkyl) or alkaryl (such as C5 to C 25 Alkaryl);

[0289] wherein at least one of R2 to R5 or R2 to R7, when present, is —CHR8OR9, for example, all of R2 to R5 or R2 to R7, when present, may be —CHR8OR9.

[0290] In the cross-linked material according to formula (III), R1 may be C1 to C 20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Arylalkyl or -NR6R7; such as C4 to C 24 Aryl or C5 to C 25 Aralkyl, or C4 to C 24 Aryl, such as C4 to C 12 Aryl, such as C6 aryl.

[0291] In the cross-linked material according to formula (III), R1 may be -NR6R7.

[0292] In the cross-linked material according to formula (III), R2 to R7, when present as appropriate, may each independently be hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl or -CHR8OR9; such as hydrogen, C1 to C 20 Alkyl or -CHR8OR9, such as hydrogen, C1 to C 10 Alkyl or -CHR8OR9; such as C1 to C5 alkyl or -CHR8OR9, such as -CHR8OR9.

[0293] In the cross-linked material according to formula (III), R2 to R7, when present as appropriate, may each independently be hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl or -CHR8OR9, such as hydrogen, C1 to C 20 Alkyl or -CHR8OR9, such as hydrogen, C1 to C 10 Alkyl or -CHR8OR9, such as C1 to C5 alkyl or -CHR8OR9, such as -CHR8OR9, and R8 can be independently hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Aralkyl, alkoxyalkyl, C2 to C 40 Alkoxyalkyl or C5 to C 25 Alkaryl, such as hydrogen, C1 to C 20 Alkyl, such as hydrogen; and R9 can be hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Aralkyl, alkoxyalkyl, C2 to C 40 Alkoxyalkyl or C5 to C25 Alkaryl, such as hydrogen, C1 to C 20 Alkyl groups, such as C1 to C 20 Alkyl, or C1 to C 10 Alkyl, or C1 to C5 alkyl, such as C1 or C2 alkyl.

[0294] The crosslinking material according to formula (III) can be the reaction product of a reaction mixture comprising a triazine, such as melamine or benzoguanamine, and formaldehyde. These concentrates can be etherified, typically with methanol, ethanol, butanol, or a mixture thereof. For the chemistry, preparation, and use of aminoplast resins, see "Chemistry and Applications of Amino Crosslinkers or Aminoplasts," Volume V, Part 11, pages 21 ff., edited by Dr. Oldring; John Wiley & Sons / Cita Technologies Ltd., London, 1998.

[0295] The cross-linking material according to formula (III) may comprise melamine or a derivative thereof, such as butylated and / or methylated melamine; and / or benzoguanamine or a derivative thereof, such as butylated and / or methylated benzoguanamine. The cross-linking material according to formula (III) may comprise benzoguanamine or a derivative thereof, such as butylated and / or methylated benzoguanamine.

[0296] Crosslinking materials may include those that are the reaction product of a reaction mixture including a triazine, such as melamine or benzoguanamine, and formaldehyde.

[0297] The cross-linking material may include benzoguanamine or a derivative thereof.

[0298] Benzoguanamine or its derivatives may include commercially available benzoguanamine or its derivatives. Suitable examples of commercially available benzoguanamine and its derivatives include, but are not limited to, benzoguanamine-formaldehyde-based materials such as those sold under the trade name CYMEL (registered trademark), such as CYMEL 1123 (available from allnex), those sold under the trade name ITAMIN (registered trademark), such as ITAMIN BG143 (available from Galstaff Multiresine), or those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL BF892 and MAPRENAL BF 892 / 68B (available from INEOS); glycoluril-based materials such as those sold under the trade name CYMEL (registered trademark), such as CYMEL 1170 and CYMEL 1172 (available from allnex); and combinations thereof.

[0299] Benzoguanamine or its derivatives may include benzoguanamine-formaldehyde-based materials sold under the trade name MAPRENAL (registered trademark).

[0300] Benzoguanamine or a derivative thereof may include MAPRENAL BF 892 and / or MAPRENAL BF 892 / 68B (commercially available from INEOS). Benzoguanamine or a derivative thereof may include MAPRENAL BF 892 / 68B (commercially available from INEOS).

[0301] The cross-linking material may be present in the coating composition in any suitable amount.

[0302] The coating composition can include at least 0.5 wt% crosslinking material based on the total solid weight of the coating composition, such as at least 1 wt%, at least 5 wt%, at least 10 wt%, or at least 15 wt% crosslinking material based on the total solid weight of the coating composition.

[0303] The coating composition can include up to 70 wt% crosslinking material based on the total solids weight of the coating composition, such as up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 25 wt%, or up to 20 wt% crosslinking material based on the total solids weight of the coating composition.

[0304] The coating composition may comprise 0.5 wt % to 90 wt %, or 1 wt % to 90 wt %, such as 1 wt % to 80 wt %, such as 1 wt % to 70 wt %, such as 1 wt % to 60 wt %, such as 1 wt % to 50 wt %, such as 1 wt % to 40 wt %, such as 1 wt % to 30 wt % or even 1 wt % to 25 wt % of the crosslinking material, based on the total solid weight of the coating composition. The coating composition may comprise 5 wt % to 90 wt %, such as 5 wt % to 80 wt %, such as 5 wt % to 70 wt %, such as 5 wt % to 60 wt %, such as 5 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt % or even 5 wt % to 25 wt % of the crosslinking material, based on the total solid weight of the coating composition. The coating composition may comprise 10 wt % to 90 wt %, such as 10 wt % to 80 wt %, such as 10 wt % to 70 wt %, such as 10 wt % to 60 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, or even 10 wt % to 25 wt % or 10 wt % to 20 wt % of the crosslinking material, based on the total solid weight of the coating composition. The coating composition may comprise 15 wt % to 90 wt %, such as 15 wt % to 80 wt %, such as 15 wt % to 70 wt %, such as 15 wt % to 60 wt %, such as 15 wt % to 50 wt %, such as 15 wt % to 40 wt %, such as 15 wt % to 30 wt %, or even 15 wt % to 25 wt % of the crosslinking material, based on the total solid weight of the coating composition.

[0305] The coating composition may further include a catalyst. Any catalyst commonly used to catalyze the crosslinking reaction between the polyester material and the crosslinking agent may be used. Suitable catalysts are well known to those skilled in the art. The catalyst may be a non-metallic or metallic catalyst or a combination thereof. Suitable non-metallic catalysts include, but are not limited to, phosphoric acid; blocked phosphoric acid; CYCAT (RTM) XK 406N (commercially available from allnex); sulfuric acid; sulfonic acid; CYCAT 600 (commercially available from allnex); NACURE (RTM) 5076 or NACURE 5925 (commercially available from King Industries); NACURE XC 235 (commercially available from King Industries); and combinations thereof. Suitable metal catalysts are well known to those skilled in the art. Suitable metal catalysts include, but are not limited to, tin-containing catalysts such as monobutyltin tris(2-ethylhexanoate); zirconium-containing catalysts such as KKAT(RTM) 4205 (commercially available from King Industries); titanate-based catalysts such as tetrabutyl titanate TnBT (commercially available from Sigma Aldrich); and combinations thereof.

[0306] Suitable examples of catalysts may include, but are not limited to, metal compounds such as stannous octoate; stannous chloride; butyl stannous acid (hydroxybutyl tin oxide); monobutyltin tris(2-ethylhexanoate); chlorobutyl stannous hydroxide; tetra-n-propyl titanate; tetra-n-butyl titanate; zinc acetate; acid compounds such as phosphoric acid; p-toluenesulfonic acid; dodecylbenzenesulfonic acid (DDBSA), such as blocked DDBSA, tetraalkyl zirconium materials, antimony trioxide, germanium dioxide, and combinations thereof. The catalyst may include dodecylbenzenesulfonic acid (DDBSA), such as blocked DDBSA.

[0307] When present, the catalyst can be used in the coating composition in any suitable amount. The catalyst can be present in the coating composition in an amount of ≥0.001% by weight of the solids of the coating composition, such as ≥0.01% by weight of the solids of the coating composition, such as ≥0.025%. The catalyst can be present in the coating composition in an amount of ≤1% by weight of the solids of the coating composition, such as ≤0.7% by weight of the solids of the coating composition, such as ≤0.5%. The catalyst can be present in the coating composition in an amount of 0.001% to 1% by weight of the solids of the coating composition, such as 0.01% to 0.7% by weight of the solids of the coating composition, such as 0.025% to 0.5%.

[0308] The coating composition may include additional resin materials. Suitable additional resin materials are well known to those skilled in the art. Suitable examples of additional resin materials include, but are not limited to, polyester resins; acrylic resins; polyvinyl chloride (PVC) resins; alkyd resins; polyurethane resins; polysiloxane resins; epoxy resins, or combinations thereof.

[0309] The coating composition may include other optional materials well known in the art of formulating coatings, such as plasticizers, wear resistant particles, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic co-solvents, reactive diluents, catalysts, grinding media, lubricants, waxes and other common adjuvants.

[0310] Suitable lubricants are well known to those skilled in the art. Suitable examples of lubricants include, but are not limited to, carnauba wax and polyethylene lubricants. The lubricant (when present) may be used in the coating composition in an amount of at least 0.01 wt % based on the total solid weight of the coating composition.

[0311] Surfactants can optionally be added to the coating composition to aid in the flow and wetting of the substrate. Suitable surfactants are well known to those skilled in the art. Surfactants (when present) are selected that are compatible with food and / or beverage container applications. Suitable surfactants include, but are not limited to, alkyl sulfates (e.g., sodium lauryl sulfate); ether sulfates; phosphate esters; sulfonates; and various alkali, ammonium, and amine salts thereof; fatty alcohol ethoxylates; alkylphenol ethoxylates (e.g., nonylphenol polyethers); salts thereof and / or combinations thereof. Surfactants (when present) can be present in an amount of 0.01 wt % to 10 wt %, such as 0.01 wt % to 5 wt %, such as 0.01 wt % to 2 wt %, based on the total solid weight of the coating composition.

[0312] The coating composition may be substantially free of, substantially free of, or completely free of bisphenol A (BPA) and its derivatives. Derivatives of bisphenol A include, for example, bisphenol A diglycidyl ether (BADGE). The coating composition may be substantially free of or completely free of bisphenol F (BPF) and its derivatives. Derivatives of bisphenol F include, for example, bisphenol F diglycidyl ether (BPFG). The above-mentioned compounds or their derivatives may not be intentionally added to the coating composition, but may be present in trace amounts due to inevitable contamination in the environment. "Substantially free" means a coating composition containing less than 1000 parts per million (ppm) of any of the above-mentioned compounds or their derivatives. "Substantially free" means a coating composition containing less than 100 ppm of any of the above-mentioned compounds or their derivatives. "Completely free" means a coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or their derivatives.

[0313] The coating composition may be substantially free, substantially free, or completely free of dialkyl tin compounds, including oxides or other derivatives thereof. Examples of dialkyl tin compounds include, but are not limited to, dibutyltin dilaurate (DBTDL); dioctyltin dilaurate; dimethyltin oxide; diethyltin oxide; dipropyltin oxide; dibutyltin oxide (DBTO); dioctyltin oxide (DOTO), or combinations thereof. "Substantially free" means a coating composition containing less than 1000 parts per million (ppm) of any of the above-mentioned compounds or their derivatives. "Substantially free" means a coating composition containing less than 100 ppm of any of the above-mentioned compounds or their derivatives. "Completely free" means a coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or their derivatives.

[0314] The coating composition may be substantially free of styrene. The coating composition may be substantially free of or may be completely free of styrene. "Substantially free" means a coating composition that contains less than 1000 parts per million (ppm) of any of the above-mentioned compounds or derivatives thereof. "Substantially free" means a coating composition that contains less than 100 ppm of any of the above-mentioned compounds or derivatives thereof. "Completely free" means a coating composition that contains less than 20 parts per billion (ppb) of any of the above-mentioned compounds or derivatives thereof.

[0315] The coating composition may be substantially free of phenol, or substantially free of phenol, or completely free of phenol. "Substantially free" means a coating composition containing less than 1000 parts per million (ppm) of any of the above-mentioned compounds or derivatives thereof. "Substantially free" means a coating composition containing less than 100 ppm of any of the above-mentioned compounds or derivatives thereof. "Completely free" means a coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or derivatives thereof.

[0316] The coating composition may be substantially free of formaldehyde, or substantially free of formaldehyde, or completely free of formaldehyde. "Substantially free" means a coating composition containing less than 1000 parts per million (ppm) of any of the above-mentioned compounds or derivatives thereof. "Substantially free" means a coating composition containing less than 100 ppm of any of the above-mentioned compounds or derivatives thereof. "Completely free" means a coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or derivatives thereof.

[0317] The coating composition can have any suitable solids content. The solids content of the coating composition can be ≥ 10%, such as ≥ 20% or ≥ 30%, by weight of the coating composition. The solids content of the coating composition can be ≤ 80%, such as ≤ 70% or ≤ 65% by weight of the coating composition. The solids content of the coating composition can be from 10% to 80%, such as from 20% to 70% or from 30% to 65% by weight of the coating composition.

[0318] The coating composition may not include 2,2,4,4-tetramethyl-1-3-cyclobutanediol ("TMCD"). The definition of the polyol component and / or diol component may exclude 2,2,4,4-tetramethyl-1-3-cyclobutanediol ("TMCD").

[0319] The substrate can be formed from any suitable material. The substrate can be a metal substrate. Suitable materials will be familiar to those skilled in the art. Suitable examples include, but are not limited to, steel; tinplate; tin-free steel (TFS); galvanized steel, such as electrogalvanized steel; aluminum; aluminum alloys; and combinations thereof. The substrate can be formed from aluminum, steel, tinplate, tin-free steel (TFS), galvanized steel (such as electrogalvanized steel), or combinations thereof. The substrate can be formed from aluminum, tinplate, or tin-free steel (TFS), typically aluminum or tinplate.

[0320] The substrate can be a package, such as a food and / or beverage package, that is at least partially coated with any of the coating compositions described herein. A "package" is any substance used to hold another article, particularly for transport from a manufacturing site to a consumer, and subsequently stored by the consumer. Therefore, a package is understood to be a sealed substance that keeps its contents from spoiling before being opened by the consumer. Manufacturers typically identify the length of time a food or beverage will not spoil, which typically ranges from several months to several years. Therefore, the "package" of the present invention is distinguished from a storage container or baking tray in which a consumer can make and / or store food; such containers will only maintain the freshness or integrity of the food product for a relatively short period of time. The package can be made of metal or non-metal, such as plastic or laminate, and can be in any form. Another example of a suitable package is a metal can. The term "metal can" includes any type of metal can, container, or any type of storage container or portion thereof that is sealed by a food and / or beverage manufacturer to minimize or eliminate the spoilage of the contents until the consumer opens such package. An example of a metal can is a food can; the term "food can" is used herein to refer to a can, container, or any type of storage container, or portion thereof, for holding any type of food and / or beverage. The term "metal can" specifically includes food cans, and also specifically includes "can ends," including "EZ ends," which are typically stamped from end stock and used in conjunction with food and beverage packaging. The term "metal can" also specifically includes metal caps and / or closures, such as bottle caps, screw-top caps, and lids of any size, bayonet caps, and the like. Metal cans can also be used to hold other items, including, but not limited to, personal care products, pesticides, spray paint, and any other compound suitable for packaging in an aerosol can. Cans can include "two-piece cans" and "three-piece cans," as well as punched, one-piece cans. Such packaging can hold, for example, food, toothpaste, personal care products, and the like.

[0321] Metal coils are widely used in many industries and are also suitable substrates for coating. Coil coatings often also include colorants.

[0322] In the above-defined uses, the coating composition is typically used to coat surfaces and parts thereof. The part may comprise multiple surfaces. The part may comprise a portion of a larger part, assembly, or device. A portion of a part may be coated with an aqueous composition or powder composition as defined herein, or the entire part may be coated.

[0323] The application of various pretreatments and coatings for packaging is relatively well established. For example, such treatments and / or coatings may be used in the case of metal cans, where they are used to delay or inhibit corrosion, provide a decorative coating, facilitate handling during manufacturing, etc. Coatings may be applied to the interior of such cans to prevent the contents from coming into contact with the metal of the container. For example, contact between the metal and the food or beverage can cause corrosion of the metal container, which in turn may contaminate the food or beverage. This is particularly true when the contents of the can are acidic in nature. Coatings applied to the interior of the metal can also help prevent corrosion in the headspace of the can, which is the area between the product fill line and the can lid; corrosion in the headspace is particularly problematic for foods with high salt content. Coatings may also be applied to the exterior of the metal can.

[0324] The substrate may be new (ie, newly constructed or manufactured) or may be refurbished.

[0325] The coating composition can be applied to a substrate or a portion thereof as a single layer or as part of a multi-layer system. The coating composition can be applied as a single layer. The coating composition can be applied to an uncoated substrate. For the avoidance of doubt, the uncoated substrate extends to a surface that is clean prior to application. The coating composition can be applied over another paint layer as part of a multi-layer system. For example, the coating composition can be applied over a primer. The coating composition can form an intermediate layer or a top coat. The coating composition can be applied as the first coating layer of a multi-coat system. The coating composition can be applied as a base coat or primer. The second, third, fourth, etc. coating layers can include any suitable paint, such as those containing, for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins, or combinations thereof. The second, third, fourth, etc. coating layers can include polyester resins. The second, third, fourth, etc. coating layers can be liquid coatings or powder coatings.

[0326] Those skilled in the art will appreciate that the coating composition can be applied before or after forming an article, such as packaging, etc. For example, the coating composition can be applied to a metal substrate that is then shaped and formed into a metal article, or the coating composition can be applied to a preformed article.

[0327] The coating composition may be applied to the substrate in one or more applications.

[0328] The coating composition can be applied to the substrate by any suitable method. Methods for applying the coating composition are well known to those skilled in the art. Suitable application methods for the coating composition include, but are not limited to, electrocoating; spraying; electrostatic spraying; dipping; roller coating; brushing, and the like.

[0329] The coating composition may be applied to any suitable dry film thickness.The coating composition may be applied to a dry film thickness of 2 to 40 micrometers (μm).

[0330] It will also be understood that the substrate can be pretreated with a pretreatment composition, such as a pretreatment solution. Non-limiting examples of pretreatment compositions include zinc phosphate pretreatment solutions (e.g., those described in U.S. Patents 4,793,867 and 5,588,989), zirconium-containing pretreatment solutions (e.g., those described in U.S. Patents 7,749,368 and 8,673,091). Other non-limiting examples of pretreatment compositions include those that include trivalent chromium, hexavalent chromium, lithium salts, permanganates, rare earth metals such as yttrium, or lanthanides such as cerium. Another non-limiting example of a suitable surface pretreatment composition is a sol-gel, such as those that include alkoxy-silanes, alkoxy-zirconates, and / or alkoxy-titanates. Alternatively, the substrate can be an untreated substrate that has not been pretreated with a pretreatment composition, such as a bare substrate.

[0331] The coating composition, pretreatment composition and / or layer deposited therefrom, such as a pretreatment layer, primer layer or topcoat layer, substrate and / or coated substrate or portion thereof, may be substantially free of hexavalent chromium compounds, meaning that hexavalent chromium or hexavalent chromium-containing compounds are not intentionally added, but may be present in trace amounts, such as due to impurities or unavoidable contamination in the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that hexavalent chromium or hexavalent chromium-containing compounds are not present in the aqueous or powder composition and / or layer deposited therefrom, as well as any pretreatment layer, primer layer or topcoat layer, at levels that would cause a burden on the environment. The coating composition, pretreatment composition and / or layer deposited therefrom, such as a pretreatment layer, primer layer or topcoat layer, substrate and / or coated substrate or portion thereof, may be substantially free of or completely free of hexavalent chromium compounds. Non-limiting examples of such chromium-containing compounds include: chromic acid, chromium trioxide, chromic anhydride; chromates such as ammonium chromate, sodium chromate, potassium chromate, as well as calcium chromate, barium chromate, magnesium chromate, zinc chromate, cadmium chromate, and strontium chromate; and dichromates such as ammonium dichromate, sodium dichromate, potassium dichromate, as well as calcium dichromate, barium dichromate, magnesium dichromate, zinc dichromate, cadmium dichromate, and strontium dichromate. The substrate or coated substrate that is substantially free of, substantially free of, or completely free of hexavalent chromium may or may not have undergone a pretreatment process. When the substrate or coated substrate undergoes a pretreatment process involving passivation, the passivation solution used may be substantially free of, substantially free of, or completely free of hexavalent chromium compounds. Thus, the passivation process may not include hexavalent chromium compounds. For example, the passivation process may not include contacting and / or immersing the substrate (e.g., tinplate sheet) with a solution comprising a hexavalent chromium compound. The substrate may include an aluminum, tin-free steel, or tinplate substrate that is substantially free, essentially free, or completely free of hexavalent chromium.

[0332] The term "substantially free" means that the coating composition and / or the layer deposited therefrom, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 10 ppm of hexavalent chromium (based on the total solids weight of the composition, layer(s), if any, respectively). The term "substantially free" means that the coating composition and / or the layer deposited therefrom, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 1 ppm of hexavalent chromium (based on the total solids weight of the composition, layer(s), if any, respectively). The term "completely free" means that the coating composition and / or the layer comprising the coating composition, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 1 ppb of hexavalent chromium (based on the total solids weight of the composition, layer(s), if any, respectively).

[0333] The present invention may include a trivalent chromium pretreated substrate, such as a trivalent chromium pretreated substrate that is substantially free of hexavalent chromium compounds. Thus, the passivation process may include a trivalent chromium compound. The trivalent chromium compound may include chromium (III) fluoride. For example, the passivation process may include contacting and / or immersing a substrate (such as a tinplate sheet) in a solution including a trivalent chromium compound. The substrate may include aluminum, tin-free steel, or tinplate as the trivalent chromium pretreated substrate.

[0334] The pretreatment composition may include an acid functional polymer and / or include phosphoric acid. The acid functional polymer may be an acid functional acrylic, such as a carboxylic acid functional acrylic.

[0335] The passivation process may include any passivation 505 or 555 method from Arcelor, Tata, TKS or US Steel, and any passivation process based on Henkel Bonderite 1456 applied by any tin mill from any country or region. Pretreatment may be performed according to Henkel NR 6207. Tinplate that is substantially free of hexavalent chromium is available from commercial sources.

[0336] The substrate may optionally be subjected to other treatments prior to coating. For example, the substrate may be cleaned, cleaned and deoxidized, positively treated, pickled, plasma treated, laser treated, or subjected to ion vapor deposition (IVD). These optional treatments may be used alone or in combination with the pretreatment composition.

[0337] The coating composition can be cured by any suitable method. The coating composition can be cured by thermal curing, radiation curing or by chemical curing, such as by thermal curing. The coating composition can be cured at any suitable temperature when thermally curing. The coating composition can be cured to a peak metal temperature (PMT) of 150°C to 350°C, such as 175°C to 320°C, such as 190°C to 300°C or even 200°C to 280°C when thermally curing. The coating composition can be cured at 210°C or at 260°C when thermally curing. For the avoidance of doubt, unless otherwise indicated, the terms "peak metal temperature" and similar terms used herein refer to the highest temperature reached by the metal substrate during exposure to heat during the thermal curing process. In other words, the peak metal temperature (PMT) is the highest temperature reached by the metal substrate, not the temperature applied thereto. Those skilled in the art will understand that the temperature reached by the metal substrate may be lower than the temperature applied thereto, or may be substantially equal to the temperature applied thereto. The temperature reached by the metal substrate may be lower than the temperature applied thereto.

[0338] Curing the coating composition may form a cured film.

[0339] For purposes of the present invention, an aliphatic group is a hydrocarbon moiety that can be straight (i.e., unbranched), branched or cyclic and can be fully saturated or contain unsaturated units but is not aromatic. The term "unsaturated" means a moiety with double bonds and / or triple bonds. Therefore, the term "aliphatic" is intended to encompass alkyl, cycloalkyl, alkenylcycloalkenyl, alkynyl or cycloalkenyl and combinations thereof. The term "(hetero)aliphatic" encompasses aliphatic groups and / or heteroaliphatic groups.

[0340] The aliphatic group is optionally C 1-30 Aliphatic groups, i.e., aliphatic groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms. Optionally, the aliphatic group is C 1-15 An aliphatic group, optionally C 1-12 aliphatic group, optionally C 1-10 aliphatic group, optionally C 1-8 Aliphatic groups, such as C 1-6 Aliphatic Groups. Suitable aliphatic groups include straight-chain or branched alkyl, alkenyl, and alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, and (cycloalkyl)alkenyl.

[0341] Heteroaliphatic groups (including heteroalkyl, heteroalkenyl and heteroalkynyl) are aliphatic groups as described above that additionally contain heteroatoms. Thus, heteroaliphatic groups optionally contain 2 to 21 atoms, optionally 2 to 16 atoms, optionally 2 to 13 atoms, optionally 2 to 11 atoms, optionally 2 to 9 atoms, optionally 2 to 7 atoms, one of which is a carbon atom. The optional heteroatom is selected from O, S, N, P and Si. When a heteroaliphatic group has two or more heteroatoms, the heteroatoms may be the same or different. A heteroaliphatic group may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and may contain saturated, unsaturated or partially unsaturated groups.

[0342] As used herein, the terms "alkyl" and "alk" refer to a saturated straight or branched chain hydrocarbon radical derived from an aliphatic moiety by removing a single hydrogen atom. 1-20Alkyl is a "linear or branched alkyl group having from 1 to 20 carbon atoms. Thus, an alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Optionally, an alkyl group is C 1-15 Alkyl, optionally C 1-12 Alkyl, optionally C 1-10 Alkyl, optionally C 1-8 Alkyl, optionally C 1-6 Specifically, "C 1-20 Examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, isopentyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1-ethylbutyl, 1-methylbutyl, 2-methylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, etc.

[0343] As used herein, the term "alkenyl" refers to a group derived from a straight or branched aliphatic moiety having a carbon-carbon double bond by removing a single hydrogen atom. As used herein, the term "alkynyl" refers to a group derived from a straight or branched aliphatic moiety having a carbon-carbon triple bond by removing a single hydrogen atom. Alkenyl and alkynyl are optionally "C 2-20 Alkenyl" and "C 2-20 Alkynyl", optionally "C 2-15 Alkenyl" and "C 2-15 Alkynyl", optionally "C 2-12 Alkenyl" and "C 2-12 Alkynyl", optionally "C 2-10 Alkenyl" and "C 2-10 Alkynyl", optionally "C 2-8 Alkenyl" and "C 2-8 Alkynyl", optionally "C 2-6 Alkenyl" and "C 2-6 Alkynyl". Examples of alkenyl groups include ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, 1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl and allyl. Examples of alkynyl groups include ethynyl, 2-propynyl (propargyl) and 1-propynyl.

[0344] As used herein, the term "alicyclic", "carbocycle" or "carbocyclic" refers to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridged and spiro-fused) ring system having 3 to 20 carbon atoms, i.e., an alicyclic group having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Optionally, the alicyclic group has 3 to 15, optionally 3 to 12, optionally 3 to 10, optionally 3 to 8 carbon atoms, optionally 3 to 6 carbon atoms. The term "alicyclic", "carbocycle" or "carbocyclic" also includes aliphatic rings fused to aromatic or non-aromatic rings, such as a tetrahydronaphthyl ring, where the point of attachment is on the aliphatic ring. The carbocyclic group can be polycyclic, for example bicyclic or tricyclic. It should be understood that the alicyclic group can include an alicyclic ring carrying an alkyl substituent that is connected or not connected, such as -CH2-cyclohexyl. Specifically, the example of carbocyclic ring includes cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2,2,1] heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro [4.5] decane, cycloheptane, adamantane and cyclooctane.

[0345] Alicyclic groups are saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridged and spiro-fused) ring systems having 3 to 20 carbon atoms, and the alicyclic groups are alicyclic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Optionally, the alicyclic groups have 3 to 15, optionally 3 to 12, optionally 3 to 10, optionally 3 to 8 carbon atoms, optionally 3 to 6 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It should be understood that alicyclic groups can include alicyclic rings with or without alkyl substituents, such as -CH2-cyclohexyl. Specifically, C 3-20 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and cyclooctyl.

[0346] Aryl or aromatic ring is a monocyclic or polycyclic ring system having 5 to 20 carbon atoms, wherein the rings in the system are aromatic, and wherein each ring in the system contains three to twelve ring members. Aryl is optionally "C 6-12 "Aryl", and is an aromatic group consisting of 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and includes fused ring groups such as monocyclic groups or bicyclic groups. Specifically, "C 6-10Examples of the “aryl group” include phenyl, biphenyl, indenyl, anthracenyl, naphthyl, azulenyl, and the like. It should be noted that fused rings such as indane, benzofuran, phthalimide, phenanthridine, and tetralin are also included in the aryl group.

[0347] As used herein, unless expressly stated otherwise, all numbers, such as those expressing values, ranges, amounts, or percentages, may be read as being preceded by the word "about," even if the term does not expressly appear. The term "about," when used herein, means + / - 10% of the stated value.

[0348] The recitation of numerical ranges by endpoints includes all integers and, where appropriate, fractions within the range (e.g., 1 to 5 includes 1, 2, 3, 4 when referring to, for example, a plurality of elements, and 1.5, 2, 2.75, and 3.80 when referring to, for example, a measurement). The recitation of endpoints also includes the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). When ranges are given, any endpoint within those ranges and / or numbers within those ranges may be combined within the scope of the invention.

[0349] The singular encompasses the plural, and vice versa. For example, although reference is made herein to "a" polyester material, "a" feathering reducer, "an" cross-linking agent, etc., one or more of each of these, as well as any other components, may be used.

[0350] As used herein, the term "polymer" refers to oligomers and both homopolymers and copolymers, and the prefix "poly" means two or more.

[0351] The terms "comprising," "for example," and similar terms mean including but not limited to. Similarly, as used herein, the terms "on," "applied on / over," "formed on / over," "deposited on / over," "covering," and "provided on / over" mean formed, covered, deposited, or provided on a surface but not necessarily in contact with the surface. For example, a coating "formed on a substrate" does not exclude the presence of one or more other coatings of the same or different composition positioned between the formed coating and the substrate.

[0352] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," or "containing," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps. In addition, although the present invention has been described in terms of "comprising," the processes, materials, and coating compositions described in detail herein may also be described as "consisting essentially of" or "consisting of." For example, although the present invention has been described in terms of a coating comprising a polyester binder material and a feathering reducer, coatings consisting essentially of and / or consisting of a polyester binder material and a feathering reducer are also within the scope of the present invention. In this case, "consisting essentially of" means that any additional coating components do not materially affect the feathering properties of the coating. If a material is described as "obtainable from," the material may also be described as "obtained from."

[0353] As used herein, when the term "and / or" is used in conjunction with a list of two or more items, it means that any one of the listed items can be used alone, or any combination of two or more of the listed items can be used. For example, if a list is described as including the group A, B, and / or C, the list can include A alone; B alone; C alone; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B, and C. For example, the coating composition may include a feathering reducer selected from the group consisting of: (i) an acrylic feathering reducer comprising a functional group selected from the group consisting of hydroxyl, epoxide, phosphated epoxide, and / or acid functional groups; (ii) a hydroxyl-functional polyester feathering reducer; (iii) a feathering reducer comprising a functional group selected from the group consisting of amine, amide, imine, and / or nitrile; (iv) a phosphated epoxy resin feathering reducer; (v) a phenolic resin feathering reducer; and / or (vi) a feathering reducer comprising an oxazolyl functional group, and the coating composition may include the following agents: (i) alone, (ii) alone, (iii) alone, (iv) alone, (v) alone, (vi) alone; a combination of (i) and (ii), a combination of (i) and (iii), a combination of (i) and (iv), a combination of (i) and (v), a combination of (i) and (vi), a combination of (i), (ii), and (iii), and the like.

[0354] Where ranges are provided in relation to a genus, each range may also apply additionally and independently to any one or more of the listed species of that genus. For example, the present invention may include from 0.1% to 40% of an acrylic feathering agent, based on the total solids weight of the composition, comprising an epoxide-functional acrylic feathering reducer, in an amount such that the composition comprises from 0.1% to 40% of the epoxide-functional acrylic feathering reducer, based on the total solids weight of the composition. Similarly, the present invention may include from 0.1% to 40% of an acrylic feathering agent, based on the total solids weight of the composition, comprising an epoxide-functional acrylic feathering reducer and an oxazolyl-functional acrylic feathering reducer, in an amount such that the composition comprises from 0.1% to 40% of each of the epoxide-functional acrylic feathering reducer and the oxazolyl-functional acrylic feathering reducer, based on the total solids weight of the composition. Another example can be where the present invention includes from 0.1% to 40% of an acrylic feathering agent, based on the total solids weight of the composition, wherein the acrylic feathering agent includes an epoxide-functional acrylic feathering reducer and an oxazolyl-functional acrylic feathering reducer, in an amount such that the composition includes ≥ 0.1% of the epoxide-functional acrylic feathering reducer, based on the total solids weight of the composition. Further, for example, the present invention can include from 0.1% to 40% of an acrylic feathering agent, based on the total solids weight of the composition, wherein the acrylic feathering agent includes an epoxide-functional acrylic feathering reducer and an oxazolyl-functional acrylic feathering reducer, in an amount such that the composition includes ≤ 20% of the epoxide-functional acrylic feathering reducer, based on the total solids weight of the composition. In addition, a species of one genus, such as epoxide-functional acrylic feathering reducer, can also be a subgenus of another subspecies, such as epoxide and hydroxyl-functional acrylic feathering reducers. For example, the present invention can include from 0.1% to 40% of an acrylic feathering agent, based on the total solids weight of the composition, the acrylic feathering agent including an epoxide functional acrylic feathering reducer, in an amount such that the composition includes from 0.1% to 40% of an epoxide functional acrylic feathering reducer, based on the total solids weight of the composition, and the epoxide functional acrylic feathering reducer includes an epoxide and a hydroxyl functional acrylic feathering reducer, in an amount such that the composition includes ≥ 0.1% of the epoxide and hydroxyl functional acrylic feathering reducer. Further examples of the foregoing include ranges provided for: polyester binder materials; hydroxyl functional polyester feathering reducers; feathering reducers including functional groups selected from amines, amides, imines, and / or nitrile; and / or phosphated epoxy feathering reducers, and all associated species, subgenera, and subspecies.

[0355] All features contained herein may be combined with any of the above in any combination.

[0356] To better understand the present invention and to show how embodiments of the present invention may be implemented, reference will now be made to the following experimental data by way of example.

[0357] Examples

[0358] Polyester 1

[0359] Polyester 1 was formed as follows.

[0360] The diols, diacids, and catalysts listed in Table 1 were added as a batch to a vessel with a steam column, distillation head, and condenser. With continuous stirring at 400 rpm and a 0.5 SCFH nitrogen blanket, the batch temperature was increased to 180°C. The batch temperature was then increased to 230°C in steps of 10°C per hour over a 5-hour period. The vapor temperature was continuously monitored, and the batch temperature was increased for each step until the vapor temperature dropped below 80°C. Once the reaction temperature reached 230°C, the acid value (AV) of the polymer (defined as the mg KOH required to neutralize 1 gram of resin) was checked every hour until the acid value dropped below 20. When the resin turned from cloudy to clear, the blanket was switched to a 0.5 SCFH sparge. Once the AV was less than 20, the sparge was switched back to the blanket, and the reaction was cooled to 150°C. MeHQ was added first, followed by maleic anhydride 10 minutes later. The reaction temperature was raised back to 220°C, the sparge was reapplied, and the resin was monitored by manual sampling and analyzed every few hours by AV measurement. Once the acid number drops below 20, the reaction is cooled to 130°C and xylene is then added through an addition funnel under a 0.5 SCFH nitrogen blanket. After the xylene is added, the reaction overhead is switched to an azeotropic distillation apparatus and additional xylene is added to the attached Dean-Stark trap. The reaction is again heated to 220°C and a 0.5 SCFH nitrogen sparge is reapplied to the reaction. The reaction is monitored by AV by taking a sample of the resin containing xylene and reducing the solids content of this material to % solids, allowing comparison with a standard bubble tube reference (Gardco provides a reference and all bubble tube samples are cooled to 25°C before analysis). This "cut viscosity" is used to assess the extent of polymerization, and the bubble tube viscosity of Z4-Z5 at 55% solids is defined as the primary target. An acid number below 10 is defined as a secondary target. Once the cut-off viscosity was reached (4 hours after the addition of xylene), the reaction was sampled to measure AV, hydroxyl value content, and molecular weight as analyzed by gel permeation chromatography (GPC) relative to polystyrene standards. The resin was cooled to 130°C and Dowanol DPM solvent was added. After 1 hour, the final solvated material was decanted and analyzed for molecular weight as analyzed by gel permeation chromatography (GPC) relative to polystyrene standards, and transition temperature as assessed by differential scanning calorimetry (DSC).

[0361] Table 1 - Polyester 1

[0362] Amount (g) Neopentyl glycol 419.40 1,4-Cyclohexanedimethanol 578.80 Isophthalic acid 821.60 Terephthalic acid 408.80 Stannous octoate 3.8550 MeHQ 0.41 Maleic anhydride 40.60 Xylene 83.30 Dowanol DPM 1098.10 Initial weight 2273.08 Theoretical water loss 274.33 Final resin weight 1998.75 solid% 62.66 Mn (number average molecular weight) 4938 Mw (weight average molecular weight) 12242 PDI 2.5 AV (96% solids, presolvated) 10.71 OH (96% solids, presolvated) 7.70 Glass transition temperature (℃) 60.00

[0363] Acrylic polyester resin

[0364] The acrylic polyester resin was formed from Polyester 1 as follows.

[0365] The amount of polyester 1 specified in Table 2 was added to a round-bottom flask and enough Dowanol DPM was added to reduce the theoretical solids to 59%. Under a 0.5 SCFH nitrogen blanket, the material was heated to 130°C with continuous stirring at 400 rpm. The methacrylic acid monomers shown in the table were mixed together and then added to the reaction via a charging funnel over a 60-minute period. After 20 minutes, a mixture of 2 / 3 of the initiators in the table was diluted with Dowanol DPM and added via a charging funnel over a 40-minute period. The separate feeds of both monomers and initiators ended simultaneously. Once this occurred, the remaining 1 / 3 initiator was diluted with Dowanol DPM and added over a 5-minute period. The reaction was maintained at 130°C for a 2-hour period. After the hold, the PGA resin was poured out and the acid value (AV) and molecular weight were analyzed relative to polystyrene standards using gel permeation chromatography (GPC).

[0366] Table 2 - Acrylic Polyester Resins

[0367] Amount (g) Polyester 1 1326.33 Methacrylic acid 40.74 Butyl methacrylate 74.69 2-Hydroxyethyl Methacrylate 20.37 Dowanol DPM 174.62 Tert-butyl peracetate, 50% solution in mineral oil 13.26 Final resin weight 1650.00 Polyester% 85.37 acrylic acid% 13.95 Initiator% 0.68 AV 22 Mn 4663 Mw 13995

[0368] An acrylic-modified polyester resin was formed into an aqueous dispersion by heating the resin to 90°C and adding dimethylethanolamine while continuously stirring at 400 rpm under a 0.5 SCFH nitrogen blanket. The mixture was stirred for 10 minutes, and then deionized water preheated to 60°C was added over a 60-minute period. The aqueous dispersion was cooled to 45°C and then filtered through a 5 μm filter bag. AV and particle size analysis were performed on the aqueous dispersion.

[0369] Table 3 - Acrylic polyester resin dispersion

[0370] Amount (g) Acrylic polyester resin 1531.57 dimethylethanolamine 35.18 Deionized water 718.92 solid% 39.72 AV 14.47 Particle size (Mastersizer, μm) 0.463

[0371] GMA acrylic resin

[0372] The GMA acrylic resin feathering reducer was formed as follows.

[0373] Polymerization was carried out in a reactor equipped with heating, stirring, and a water-cooled reflux condenser. Nitrogen was sparged into the reactor to provide an inert atmosphere. 488.41 grams of butyl cellosolve and 134.37 grams of n-butanol were added to the reactor and heated to reflux at a temperature of 150 to 160°C with stirring. Separately, a monomer mixture containing 800.00 grams of glycidyl methacrylate, 464.00 grams of isobutyl methacrylate, 16 grams of 2-ethylhexyl methacrylate, and 320 grams of 4-hydroxybutyl acrylate, and an initiator mixture comprising 106.67 grams of tert-butyl peroxy-2-ethylhexanoate and 106.67 grams of butyl cellosolve were prepared and added to the monomer and initiator tanks, respectively. The monomer mixture was added to the reactor at 150°C over a period of 150 minutes. The initiator mixture was added to the reactor at the same temperature, but over a period of 180 minutes, with the initiator mixture being added 5 minutes after the monomer mixture had already been added to the reactor. At the end of the monomer feed, the monomer tank was rinsed with 65 grams of Dowanol DPM. At the end of the initiator feed, the reactor was cooled to 130°C and held at 130°C for 30 minutes. After the hold, a chaser (a mixture of 16.00 grams of tert-butyl peroxy-2-ethylhexanoate and 32.00 grams of butyl cellosolve) was added over a period of 30 minutes, followed by the addition of 67.20 grams of Dowanol DPM for rinsing. The reactor was then held at 130°C for 60 minutes. After this time, the reactor (containing the reaction mixture) was cooled by removing heat.

[0374] The resulting acrylic prepolymer was then removed from the reactor while hot. The acrylic prepolymer had a solids weight of 65.1% and a Tg of 27°C.

[0375] Table 4 - GMA acrylic acid

[0376]

[0377]

[0378] Comparative Example 1 and Examples 1 to 4 were prepared by mixing the materials of Table 5 with a mixing blade for 15 minutes.

[0379] The coated panels were obtained by drawing the coating composition onto trivalent chromium pretreated NR6207 aluminum panels (AA5182 alloy) using a wire-wound rod to obtain a dry coating weight of approximately 6.5 to 7.0 mg / square inch (msi). The coated panels were then immediately placed into a three-zone gas-fired conveyor oven for 10 seconds and baked to a peak metal temperature of 465°F (240.5°C).

[0380] Table 5 - Coating Composition

[0381]

[0382]

[0383] 1 Solvents from The Dow Chemical Company

[0384] 2 Silicone-free wetting agents from allnex

[0385] 3 Benzoguanamine resin from allnex

[0386] 4 Capped catalyst from King

[0387] 5 Microcrystalline wax from Michelman

[0388] 6 Anionic oxidized polyethylene emulsion from BYK

[0389] 7 Oxazoline-functional resins from Nippon Shokubai Co., Ltd.

[0390] 8 OH-functional polyester resins from Evonik Industries

[0391] 9 Ethylene glycol containing 10% dicyandiamide

[0392] Feathering: The feathering properties of the coatings were evaluated by Test Protocol 1 described above.

[0393] Wedge Bend: The coating's flexibility is evaluated using the wedge bend test. Coated panels are cut into 2-inch by 4-inch pieces, with the substrate grain extending perpendicular to the long length of the cut panel. They are then bent along the long length of the panel over a 1 / 8-inch metal rod, with the coated side facing outward. The bent coupons are then placed on a metal block into which wedges have been pre-cut, with the wedges tapering from 0 to 1 / 8 inch along their 4-inch length. Once placed in the wedges, each bent coupon is struck with a 4-pound metal block from a height of 12 inches to form a wedge shape, with one end of the coated metal striking itself and a 1 / 8-inch space remaining on the opposite end. The wedge-bend panels are then placed in an aqueous solution of copper sulfate and hydrochloric acid for one minute to intentionally etch the aluminum panel in areas of coating failure and cracking. The etched wedge-bend panels are then examined microscopically at 10x magnification to determine how far along the bend radius from the impact end the coating cracks. The flexibility results are reported as the length of the rupture zone starting from the impact end or as a percentage of the rupture zone relative to the total length of the wedge-bend panel.

[0394] Blushing: The coating's ability to resist blushing and adhere to aluminum panels was evaluated in a deionized water retort test. The coated panels were cut into 2-inch by 4-inch pieces, half immersed in deionized water, and then placed in a steam retort at 250°F for 30 minutes. The panels were then cooled in deionized water, dried, and immediately rated for blushing and adhesion. Blushing was visually rated on a scale of 1-10, with a rating of "10" indicating no blushing and a rating of "0" indicating complete whitening of the film.

[0395] The results of these tests are reported in Table 6.

[0396] Table 6 - Coating properties

[0397] Feathering Comparative Example 1 0.95 Example 1 0.37 Example 2 0.08 Example 3 0.32 Example 4 0.00

[0398] Table 7 - Coating properties

[0399] Wedge bend (mm) White Comparative Example 1 3 5.5 Example 1 5 4.5 Example 2 7 5.0 Example 3 5 5.5

[0400] Polyester 2

[0401] Polyester 2 was prepared as follows.

[0402] Set the packed column and top temperature of the reactor, open the condenser, and sparge nitrogen. Charges 1, 2, 3, and 4, as detailed in Table 8, are added to the reactor. The reactor is slowly heated to 160°C (320°F). The temperature is then increased to a maximum reactor temperature of 245°C (473°F), not allowing the column temperature to exceed 96°C (205°F). A steady distillation rate is maintained until the material is clear and shows an acid number of 5 or less. The material is then cooled to 160°C (320°F). Charges 5, 6, 7, 8, and 9 are then added to the reactor, and the reactor is heated to 200°C (392°F). The temperature is then increased to a maximum reactor temperature of 245°C (473°F), not allowing the column temperature to exceed 96°C (206°F). A steady distillation rate is maintained until the material is clear and shows an acid number of 20 or less. The reactor temperature is then reduced to 180°C. Charge 10 is then pumped into the reactor. A azeotropic distillation was set up above the packed column and the decanter was filled with Aromatic 100. Without exceeding 245°C, the temperature was increased to maintain a steady reflux. In-process samples were cut at the following ratio: 10 gram sample from the reactor (at 96% solids) containing 7.32 grams of N-methyl-2-pyrrolidone to 55% solids. The material was processed until it showed an acid number of 4.00 in solution and a viscosity of Z6+. The temperature was then reduced to 160°C (320°F) and charges 11, 12 and 13 were then slowly added and allowed to mix for 1 hour. The material was then filtered through a 5 micron bag. The resulting number average molecular weight of this polyester was 12,063.

[0403] Table 8 - Polyester 2

[0404] Charge number type Components quantity Charge 1 reactants 2-Methyl-1,3-propanediol 539.26 Charge 2 catalyst Tetra-n-butyl titanate 2.5 Charge 3 reactants 2,6-Dimethyl naphthalate 883.76 Charge 4 reactants Trimethylolpropane 11.62 Charge 5 reactants Isophthalic acid 615.78 Charge 6 reactants 2-Methyl-1,3-propanediol 381.91 Charge 7 reactants Adipic acid 331.95 Charge 8 reactants Maleic anhydride 32.2 Charge 9 catalyst Stannous 2-ethylhexanoate 1.4 Charge 10 solvent Aromatic Solvent-100 Type 612 Charge 11 solvent Aromatic Solvent-100 Type 147.4 Charge 12 solvent 2-Butoxyethanol 750 Charge 13 solvent Methyl ether propylene glycol acetate 490

[0405] Acidic polyester additives

[0406] The acidic polyester additive was prepared as follows:

[0407] Trimethylolpropane and 2-methyl-1,3-propanediol were charged to a reaction vessel equipped with an agitator, a nitrogen blanket, and a distillation apparatus and heated to 50°C. Once this temperature was reached, isophthalic acid, dibutyltin oxide, maleic anhydride, and phthalic anhydride were then added to the vessel and slowly heated to distillation. The mixture was esterified under a nitrogen atmosphere at a temperature of 180°C to 240°C over a period of twelve (12) hours. When the acid value of the mixture dropped to 13.00 mg KOH / g, the mixture was cooled to 160°C and then combined with Aromatic 100 solvent (i.e., an aromatic hydrocarbon solvent blend commercially available from ExxonMobil) for azeotropic distillation of water that precipitated as a condensate by-product. Thereafter, phosphoric acid solution and water were added, and azeotropic distillation of water was continued until the acid value of the mixture dropped below 20 mg KOH / g. The resulting phosphorylated polyester resin was then dissolved in 2-butoxyethanol and monobutyl ether of diethylene glycol to produce a 50% by weight solids composition.

[0408] The number average molecular weight of the resulting phosphorylated polyester was 4,500, the acid number was 20, and the hydroxyl number was 80 based on resin solids. The equivalent ratio of P—OH to OH in the polyester was 1:2.3.

[0409] Table 9 - Acidic Polyester Additives

[0410] Components parts by weight 2-Methyl-1,3-propanediol 19.9 Trimethylolpropane 3.01 Isophthalic acid 14.35 Dibutyltin oxide (catalyst) 0.06 Maleic anhydride 8.35 Phthalic anhydride 7.3 Aromatic 100 7.79 Phosphoric acid (85%) 1.11 water 0.08 2-Butoxyethanol 4.26 Diethylene glycol monobutyl ether 33.8

[0411] Phosphated epoxy resin

[0412] The phosphorylated epoxy resin feathering reducer was prepared as follows:

[0413] 16.81 g of 85% orthophosphoric acid and 28.24 g of butanol were added to the flask. The mixture was heated to 230°F (110°C) under a nitrogen inert blanket. When this temperature was reached, the nitrogen blanket was turned off and a premix of 83.19 g of cyclohexane dimethyl diglycidyl ether and 45.06 g of butanol was added over a period of 2 hours and 10 minutes. During the addition, the batch temperature was maintained below 245°F (118°C). After the feeds were complete, 4.36 g of butanol was added to the flask and the temperature was lowered to 219°F (104°C) and held for another 2 hours. An additional 22.34 g of butanol was then added to the flask.

[0414] Table 10 - Phosphorylated Epoxy Resins

[0415] type Components quantity reactants Cyclohexane dimethyl diglycidyl ether 83.19 reactants Orthophosphoric acid (85%) 16.81 solvent n-Butanol 100.0

[0416] Acid Functional Acrylic

[0417] The acid functional acrylic acid was prepared as follows.

[0418] 374g of Dowanol PM (available from Dow) and 150g of isopropyl alcohol were placed in a reaction vessel equipped with a stirrer, nitrogen blanket, and condenser, and heated to reflux at 100°C. The monomers provided in Table 2, 12.27g of t-butyl peroxyoctanoate, and 17.76g of Dowanol PM were then added to the reaction vessel under stirring over a period of 180 minutes. After this time, 17.05g of Dowanol PM was added, and the reaction mixture was held at 100°C for 15 minutes. A mixture of 2.18g of t-butyl peroxyoctanoate and 22.93g of Dowanol PM was then added at 50vol%, and the reaction mixture was held for another 60 minutes. After this time, the remaining 50vol% of the t-butyl peroxyoctanoate / Dowanol PM mixture was added along with 13.95g of Dowanol PM rinse, and the reaction mixture was again held for 60 minutes. Then, the heat was removed, 164.01 g of Dowanol PM was added to the reaction vessel, and the reaction mixture was cooled to 35°C.

[0419] The resulting acrylic resin was then removed from the reaction vessel by pouring it into a glass jar. Table 11 provides the acid values ​​of the resulting acrylic resin.

[0420] Table 11 - Acid Functional Acrylics

[0421]

[0422] For the avoidance of doubt, MAA is methacrylic acid, AA is acrylic acid, MA is methacrylate, and BMA is butyl methacrylate.

[0423] Phosphated epoxy acrylate

[0424] Phosphorylated epoxy acrylate was prepared as follows.

[0425] Epoxy functional acrylic resin. Charge No. 1 (solvent mixture) of Table 12 was charged into a suitable reaction vessel equipped with a reflux condenser, a thermocouple, and a nitrogen blanket adapter and heated to 100-105°C. Charge No. 3 (monomer mixture GMA / STY / HEMA containing GMA) and Charge No. 2 (initiator) were added to the vessel simultaneously over a 3-hour period. After the feed polymerization was complete, additional initiator was added as Charge No. 4 and the reaction was continued for two hours to complete the conversion of the residual monomer. After the hold, heating was stopped and Charge No. 5 (butyl cellosolve) was added to adjust the solids to 62.1%. The epoxy equivalent weight (EEW) of the solution mixture was determined to be 3,000 in solution. The Mw of the epoxy functional acrylic was 24,304 Da and the Mn was 7,834 Da.

[0426] Table 12-GMA acrylic resin

[0427]

[0428]

[0429] Phosphating Epoxy Acrylic Acid. The epoxy-functional polymer thus formed is then reacted with phosphoric acid. Charge No. 1 (solvent mixture) from Table 13 is charged into a suitable reaction vessel equipped with a reflux condenser, thermocouple, and adapter nitrogen blanket, followed by Charge No. 2 (phosphoric acid / butyl cellosolve mixture) and the batch heated to 120°C. When the batch reaches the desired temperature, Charge No. 3 (epoxy-functional acrylic acid) is added over a period of 1 hour. After the addition is complete, Charge No. 4 is added as a rinse and the batch is reheated to 125°C for 2 hours. After the hold, the batch is cooled to 100°C and Charge No. 5, DI water, is added dropwise. After the addition is complete, the batch is held at reflux for an additional two hours. After the two-hour hold, the batch is cooled and the EEW of the mixture is measured to confirm that the phosphorylation of the epoxy resin is complete. The resin EEW is >100,000.

[0430] Table 13 - Phosphated Epoxy Acrylate

[0431] Loading Components weight% No. 1 Butanol 280 Carbitol 120 No. 2 Phosphoric acid (85%) 12.20 Butyl cellosolve 25.0 No. 3 Epoxy functional acrylic 876 No. 4 Butanol 106 PM acetate 108 No. 5 DI water 50

[0432] Coating composition

[0433] The compositions of Comparative Examples 2 to 4 and Examples 5 to 8 were prepared by mixing the materials of Table 14 with a mixing blade for 15 minutes.

[0434] The coated panels were obtained by drawing the coating composition onto trivalent chromium pretreated NR6207 aluminum panels (AA5182 alloy) using a wire-wound rod to obtain a dry coating weight of approximately 6.5 to 7.5 mg / square inch (msi). The coated panels were then immediately placed into a three-zone gas-fired conveyor oven for 10 seconds and baked to a peak metal temperature of 465°F (240.5°C).

[0435] Table 14 - Coating Composition

[0436]

[0437] 1 A hydroxymethyl type n-butyl benzoguanamine formaldehyde resin. 68% soluble in n-butanol. From INEOS

[0438] 2 CAS 8017-16-1

[0439] 3 Carnauba wax from Michelman.

[0440] 4 PTFE-modified polyethylene wax from Lubrizol

[0441] 5 Polymeric non-silicone flow and wetting additives from Dynoadd

[0442] Feathering: The feathering properties of the coatings were evaluated by Test Protocol 1 described above.

[0443] Blushing and Adhesion: The coatings were evaluated for their ability to resist blushing and adhere to aluminum panels in a deionized water retort test. The coated panels were cut into 2 inch by 4 inch pieces, half immersed in deionized water, and then placed in a steam retort at 250°F for 30 minutes. The panels were then cooled in deionized water, dried, and immediately rated for blushing and adhesion. Blushing was visually rated using a scale of 1-10, where a rating of "10" indicates no blushing and a rating of "0" indicates complete whitening of the film. Adhesion testing was conducted according to ASTM D 3359 Test Method B using Scotch 610 tape and rated using a scale of 0-100%, where "100%" indicates no adhesion failure and "0" indicates complete adhesion failure. Tables 15 and 16 report the results of these tests.

[0444] Wedge Bend: The coating's flexibility is evaluated using the wedge bend test. Coated panels are cut into 2-inch by 4-inch pieces, with the substrate grain extending perpendicular to the long length of the cut panel. They are then bent along the long length of the panel over a 1 / 8-inch metal rod, with the coated side facing outward. The bent coupons are then placed on a metal block into which wedges have been pre-cut, with the wedges tapering from 0 to 1 / 8 inch along their 4-inch length. Once placed in the wedges, each bent coupon is struck with a 4-pound metal block from a height of 12 inches to form a wedge shape, with one end of the coated metal striking itself and a 1 / 8-inch space remaining on the opposite end. The wedge-bend panels are then placed in an aqueous solution of copper sulfate and hydrochloric acid for one minute to intentionally etch the aluminum panel in areas of coating failure and cracking. The etched wedge-bend panels are then examined microscopically at 10x magnification to determine how far along the bend radius from the impact end the coating cracks. The flexibility results are reported as the length of the fractured area starting from the impact end or as a percentage of the fractured area relative to the total length of the wedge-bend panel. The results of these tests are reported in Table 16.

[0445] Table 15 - Coating Properties

[0446]

[0447] Table 16 - Coating Properties

[0448]

[0449] Attention is directed to all papers and documents which are filed concurrently with or prior to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0450] All features disclosed in this specification (including any accompanying claims, abstract and drawings) and / or all steps of any method or process so disclosed may be combined in any combination, except combinations where at least some of these features and / or steps are mutually exclusive.

[0451] Each feature disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by an alternative feature serving the same, equivalent, or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0452] The invention is not limited to the details of the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification (including any accompanying claims, abstract and drawings) or to any novel step or any novel combination of steps in any method or process so disclosed.

Claims

1. A coated substrate comprising a coating extending over at least a portion of the substrate, wherein the coating is obtainable from a coating composition comprising: a. polymer binder; as well as b. a feathering reducer comprising a carboxylic acid reactive functional group, The coated portion of the substrate comprises a pretreatment layer, wherein the pretreatment layer is obtainable from a pretreatment composition comprising a trivalent chromium compound and being substantially free of a hexavalent chromium compound.

2. The coated substrate of claim 1, wherein the composition is an aqueous coating composition.

3. The coated substrate of claim 1, wherein the composition is an organic solvent-based coating composition.

4. The coated substrate of claim 1, wherein the polymeric binder comprises a polyester binder material.

5. The coated substrate of claim 4, wherein the polyester binder material comprises a polyester obtainable by polymerizing a polyacid component and a polyol component.

6. The coated substrate of claim 5, wherein the polyacid comprises: Maleic acid; Fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanedioic acid; dodecanedioic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexanedicarboxylic acid; Chlorendic anhydride; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; tricyclodecane polycarboxylic acid; endomethylenetetrahydrophthalic acid; endomethylenehexahydrophthalic acid; cyclohexanetetracarboxylic acid; cyclobutanetetracarboxylic acid; or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms; or esters and / or anhydrides of all the foregoing acids; or a combination of any of the foregoing polyacids and / or esters and / or anhydrides.

7. The coated substrate of claim 5, wherein the polyacid comprises terephthalic acid (TPA), dimethyl terephthalate, isophthalic acid (IPA), dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, maleic anhydride, fumaric anhydride; or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms; or a combination of any of the foregoing polyacids and / or anhydrides.

8. The coated substrate of claim 5, wherein the polyacid comprises terephthalic acid, isophthalic acid, dimethyl terephthalate, hexahydrophthalic anhydride, cyclohexane 1,4-dicarboxylic acid, maleic anhydride; or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms; or a combination of any of the foregoing polyacids and / or anhydrides.

9. The coated substrate of claim 5, wherein the polyol comprises: Ethylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol; neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; 1,2-propylene glycol; 1,3-propylene glycol; butyl ethyl propanediol; 2-methyl-1,3-propanediol; 2-ethyl-2-butyl-1,3-propanediol; 1,4-butanediol; 1,3-butanediol; 2-ethyl-1,4-butanediol; trimethylpentanediol; 2-Methylpentanediol; cyclohexanedimethanol; 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD); caprolactone diol; hydroxyalkylated bisphenol; polyether polyol; poly(oxytetramethylene) glycol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; dimethylolcyclohexane; glycerol; sorbitol; isosorbide; or a polyol monomer having an aliphatic group containing at least 15 carbon atoms; or a combination of any of the foregoing polyols.

10. The coated substrate of claim 5, wherein the polyol comprises: Ethylene glycol; 1,2-Propanediol; 1,3-Propanediol; 1,2-Butanediol; 1,3-Butanediol; 1,4-Butanediol; 2-Butane-1,4-diol; 2,3-Butanediol; 2-Methyl-1,3-Propanediol; 2,2'-Dimethyl-1,3-Propanediol (neopentyl glycol); 1,5-Pentanediol; 3-Methyl-1,5-Pentanediol; 2,4-Diethyl-1,5-Pentanediol; 1,6-Hexanediol; 2-Ethyl-1, 3-Hexanediol; 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4-trimethyl-1,3-pentanediol (TMPD), diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; isosorbide; 1,4-cyclohexanediol; or 1,1'-isopropylidene-bis(4-cyclohexanol); or a combination of any of the foregoing polyols.

11. The coated substrate of claim 5, wherein the polyol comprises ethylene glycol (EG), 1,2-propylene glycol (PG), 2-methylpropylene glycol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), butylethylpropylene glycol (BEPD), trimethylolpropane (TMP), or 1,6-hexanediol, or a combination of any of the foregoing polyols.

12. The coated substrate of claim 5, wherein the polyester binder material comprises an acrylic polyester resin.

13. The coated substrate according to claim 12, wherein the acrylic polyester resin is obtainable by grafting an acrylic polymer and a polyester resin, wherein the polyester resin is obtainable by polymerizing: i) a polyacid component; and ii) a polyol component, And wherein one of the polyacid component or the polyol component includes a functional monomer operable to impart functional groups to the polyester resin, such that an acrylic polymer can be grafted to the polyester resin by using the functional groups.

14. The coated substrate of claim 13, wherein the functional monomer of the polyester resin of the acrylic polyester resin comprises maleic acid, maleic anhydride, or fumaric acid, or a combination of any of the foregoing functional monomers.

15. The coated substrate of claim 13, wherein the acrylic polymer comprises an acrylic monomer comprising methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid, dimethylaminoethyl methacrylate, butylaminoethyl (meth)acrylate, ethylene glycol phosphate methacrylate, or a combination of any of the foregoing acrylic monomers.

16. The coated substrate of claim 13, wherein the acrylic polymer comprises an acrylic monomer comprising methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, dimethylaminoethyl methacrylate, butylaminoethyl (meth)acrylate, ethylene glycol phosphate methacrylate, or a combination of any of the foregoing acrylic monomers.

17. The coated substrate of claim 1, wherein the composition comprises ≥ 40% of the polymeric binder, based on the total solids weight of the composition.

18. The coated substrate of claim 1, wherein the feathering reducing agent comprises a functional group selected from the group consisting of hydroxyl, epoxide, acid functionality, amine, amide, imine, nitrile, and / or oxazolyl.

19. The coated substrate of claim 18, wherein the epoxide is a phosphated epoxy resin.

20. The coated substrate of claim 1, wherein the feathering reducer comprises: i. an acrylic feathering reducing agent comprising a functional group selected from the group consisting of: hydroxyl, epoxide, phosphated epoxide and / or acid functional groups; ii. Hydroxy-functional polyester feathering reducer; iii. feathering reducing agent comprising a functional group selected from: amines, amides, imines and / or nitriles; iv. Phosphated epoxy resin feathering reducer; v. Phenolic resin feathering reducers; or vi. Feathering reducing agent comprising an oxazolyl functional group; or A combination of any of the foregoing feathering reducers (i)-(vi).

21. The coated substrate of claim 20, wherein the acrylic feathering reducer (i) comprises an acrylic copolymer.

22. The coated substrate of claim 21, wherein the acrylic copolymer is formed from a monomer comprising a (meth)acrylate monomer or (meth)acrylic acid, optionally with another vinyl monomer.

23. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; propyl (meth)acrylate; butyl (meth)acrylate; cyclohexyl (meth)acrylate; benzyl methacrylate; 2-ethylhexyl (meth)acrylate; isobornyl (meth)acrylate; lauryl (meth)acrylate; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate; hydroxybutyl (meth)acrylate; ethylene glycol phosphate methacrylate; or glycidyl (meth)acrylate; or a combination of any of the foregoing monomers.

24. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers including a crosslinking monomer comprising: Allyl (meth)acrylate; divinylbenzene; ethylene glycol dimethacrylate; ethylene glycol di(meth)acrylate; 1,4-butylene glycol dimethacrylate; 1,4-butylene glycol diacrylate; 1,6-hexanediol dimethacrylate; or 1,6-hexanediol diacrylate, or a combination of any of the foregoing crosslinking monomers.

25. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising a glycidyl-functional (meth)acrylate monomer and optionally a hydroxy-functional monomer.

26. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising methyl methacrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl methacrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, or glycidyl methacrylate (GMA), or a combination of any of the foregoing monomers.

27. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising a glycidyl-functional (meth)acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, or hydroxyethyl methacrylate, or a combination of any of the foregoing monomers.

28. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising glycidyl functional acrylate, isobutyl methacrylate, ethylhexyl acrylate, or 4-hydroxybutyl acrylate, or a combination of any of the foregoing monomers.

29. The coated substrate of claim 21, wherein the acrylic copolymer comprises hydroxyl and epoxide groups.

30. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising > 10 wt% hydroxyl functional monomers, based on the total weight of monomers.

31. The coated substrate of claim 21, wherein the acrylic copolymer is formed from monomers comprising ≥ 25% glycidyl-functional monomers, based on the total weight of monomers.

32. The coated substrate of claim 20, wherein the phosphorylated epoxy acrylate feathering reducer (i) is the reaction product of a reaction mixture comprising an epoxy functional acrylic and a phosphoric acid source, a phosphonic acid source, or a combination thereof.

33. The coated substrate of claim 32, wherein the epoxy functional acrylic is formed from monomers comprising a glycidyl functional acrylate monomer and a hydroxyl functional monomer.

34. The coated substrate of claim 32, wherein the epoxy functional acrylic is formed from monomers comprising ≥ 20% hydroxyl functional monomers, based on the total weight of monomers, and / or the epoxy functional acrylic is formed from monomers comprising ≥ 2% glycidyl functional acrylate monomers, based on the total weight of monomers.

35. The coated substrate of claim 32, wherein the epoxy functional acrylic is formed from monomers comprising a glycidyl functional (meth)acrylate monomer, a hydroxyl functional monomer, and a cyclic group containing monomer.

36. The coated substrate of claim 32, wherein the reactants comprise ≥ 80% epoxy functional acrylic based on the combined weight of the phosphoric acid source and the epoxy functional acrylic.

37. The coated substrate of claim 20, wherein the acid-functional acrylic feathering reducer (i) comprises a carboxyl group.

38. The coated substrate of claim 20, wherein the acid functional acrylic feathering reducer (i) has an acid value of at least 50 mg KOH / g.

39. The coated substrate of claim 20, wherein the composition comprises an acrylic feathering reducer (i) in an amount ≥ 0.1% by weight of the solids of the coating composition.

40. The coated substrate of claim 20, wherein the composition comprises an acrylic feathering reducer (i) in an amount of ≤ 40% by weight of the solids of the coating composition.

41. The coated substrate of claim 20, wherein the composition comprises the phosphated epoxy acrylic feathering reducer and / or the acid functional acrylic feathering reducer (i) in an amount ≥ 1% based on the total solid weight of the coating composition.

42. The coated substrate of claim 20, wherein the hydroxyl-functional polyester feathering reducer (ii) comprises a polyester obtainable by polymerizing a polyacid component and a polyol component.

43. The coated substrate of claim 42, wherein the polyacid comprises: Phthalic acid; Isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic acid; hexahydrophthalic acid; maleic acid; succinic acid; itaconic acid; dimethyl isophthalate; dimethyl terephthalate; dimethyl 1,4-cyclohexanedicarboxylic acid; dimethyl 2,6-naphthalene dicarboxylic acid; dimethyl fumarate; dimethyl orthophthalate; dimethyl succinate; dimethyl glutarate; dimethyl adipate; or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms; or esters and / or anhydrides of all the foregoing acids; or a combination of any of the foregoing polyacids and / or esters and / or anhydrides.

44. The coated substrate of claim 42, wherein the polyacid comprises terephthalic acid (TPA), dimethyl terephthalate, isophthalic acid (IPA), dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, maleic anhydride, fumaric anhydride; or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms, or a combination of any of the foregoing polyacids and / or anhydrides.

45. The coated substrate of claim 42, wherein the polyacid comprises isophthalic acid, dimethyl terephthalate, hexahydrophthalic anhydride, cyclohexane 1,4-dicarboxylic acid, and / or a polyacid monomer having an aliphatic group containing at least 15 carbon atoms, or a combination of any of the foregoing polyacids and / or anhydrides.

46. ​​The coated substrate of claim 42, wherein the polyol comprises: Ethylene glycol; 1,2-Propanediol; 1,3-Propanediol; 1,2-Butanediol; 1,3-Butanediol; 1,4-Butanediol; 2-Butane-1,4-diol; 2,3-Butanediol; 2-Methyl-1,3-Propanediol; 2,2'-Dimethyl-1,3-Propanediol (neopentyl glycol); 1,5-Pentanediol; 3-Methyl-1,5-Pentanediol; 2,4-Diethyl-1,5-Pentanediol; 1,6-Hexanediol; 2-Ethyl-1,5-Propanediol 1,3-hexanediol; 2,2,4,4-tetraalkylcyclobutane-1,3-diol; 2,2,4-trimethyl-1,3-pentanediol (TMPD); diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; isosorbide; 1,4-cyclohexanediol; or 1,1'-isopropylidene-bis(4-cyclohexanol), or a combination of any of the foregoing polyols.

47. The coated substrate of claim 46, wherein the 2,2,4,4-tetraalkylcyclobutane-1,3-diol is 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD).

48. The coated substrate of claim 42, wherein the polyol comprises: trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; glycerol; or sorbitol, or a combination of any of the foregoing polyols.

49. The coated substrate of claim 42, wherein the polyol comprises ethylene glycol (EG), 1,2-propylene glycol (PG), 2-methylpropylene glycol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), butylethylpropylene glycol (BEPD), trimethylolpropane (TMP), or 1,6 hexanediol, or a combination of any of the foregoing polyols.

50. The coated substrate of claim 20, wherein the hydroxyl-functional polyester feathering reducer (ii) has a total hydroxyl value (OHV) of ≥ 65 mg KOH / g.

51. The coated substrate of claim 20, wherein the hydroxyl-functional polyester feathering reducer (ii) has a total hydroxyl value (OHV) of ≥ 80 mg KOH / g.

52. The coated substrate of claim 20, wherein the composition comprises a hydroxyl functional polyester feathering reducer (ii) in an amount ≥ 0.1% by weight of the solids of the coating composition.

53. The coated substrate of claim 20, wherein the composition comprises a hydroxyl functional polyester feathering reducer (ii) in an amount of ≤ 40% by weight of the solids of the coating composition.

54. The coated substrate of claim 20, wherein the feathering reducer (iii) comprises at least two different types of groups selected from the group consisting of amines, amides, imines, nitriles, and / or hydroxyl groups.

55. The coated substrate of claim 20, wherein the feathering reducer (iii) comprises an amine group as well as an amide group, an imine group, a nitrile group, and / or a hydroxyl group.

56. The coated substrate of claim 20, wherein the feathering reducer (iii) comprises at least two amine groups.

57. The coated substrate of claim 20, wherein the feathering reducer (iii) is a small molecule.

58. The coated substrate of claim 20, wherein the feathering reducing agent (iii) comprises dicyandiamide (DICY), 2,4,6-tris(dimethylaminomethyl)phenol and / or hydroxyalkylamides and derivatives thereof.

59. The coated substrate of claim 20, wherein the feathering reducer (iii) is a polyamide.

60. The coated substrate of claim 59, wherein the polyamide feathering reducing agent (iii) has an amine value of ≥ 150 mg KOH / gram resin.

61. The coated substrate of claim 20, wherein the composition comprises a feathering reducer (iii) in an amount ≥ 0.001% by weight of the solids of the coating composition.

62. The coated substrate of claim 20, wherein the composition comprises a feathering reducer (iii) in an amount of ≤ 5% by weight of the solids of the coating composition.

63. The coated substrate of claim 20, wherein the phosphorylated epoxy resin feathering reducer (iv) is the reaction product of a reaction mixture comprising a polyepoxide and a phosphoric acid source, a phosphonic acid source, or a combination thereof.

64. The coated substrate of claim 63, wherein the reactants comprise ≥ 70% polyepoxide based on the combined weight of the phosphoric acid source and the polyepoxide.

65. The coated substrate of claim 20, wherein the composition comprises a feathering reducer (iv) in an amount ≥ 0.1% by weight of the solids of the coating composition.

66. The coated substrate of claim 20, wherein the composition comprises a feathering reducer (iv) in an amount of ≤ 40% by weight of the solids of the coating composition.

67. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) has an aliphatic hydroxyl equivalent weight of ≥ 60.

68. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) has an aliphatic hydroxyl equivalent weight of ≥ 80.

69. The coated substrate of claim 20, wherein the phenolic feathering reducing agent (v) has an aliphatic hydroxyl equivalent weight of ≥ 90.

70. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) has an aliphatic hydroxyl equivalent weight of ≤ 500.

71. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) has an aliphatic hydroxyl equivalent weight of ≤ 200.

72. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) has an aliphatic hydroxyl equivalent weight of ≤ 160.

73. The coated substrate of claim 20, wherein the phenolic feathering reducer (v) is substantially non-alkylated at the aliphatic hydroxyl groups.

74. The coated substrate of claim 20, wherein the phenolic feathering reducing agent (v) comprises a resin that is a reaction product of a reaction mixture comprising phenol or a derivative thereof and an aldehyde.

75. The coated substrate of claim 74, wherein the phenol or derivative reactant comprises phenol and cresol.

76. The coated substrate of claim 74, wherein the phenol or derivative thereof reactant comprises ≥ 80% phenol based on the combined weight of all phenol or derivative thereof reactants.

77. The coated substrate of claim 20, wherein the phenolic feathering reducing agent (v) is a resol type phenolic.

78. The coated substrate of claim 20, wherein the phenolic feathering reducing agent (v) is water miscible.

79. The coated substrate of claim 20, wherein the composition comprises a phenolic feathering reducing agent (v) in an amount ≥ 0.1% by weight of the solids of the coating composition.

80. The coated substrate of claim 20, wherein the composition comprises a phenolic feathering reducer (v) in an amount of ≤ 40% by weight of the solids of the coating composition.

81. The coated substrate of claim 20, wherein the feathering reducing agent (vi) comprising an oxazolyl functional group has a pH of 7 to 11.

82. The coated substrate of claim 20, wherein the feathering reducer (vi) comprising an oxazolyl functional group has an oxazoline value > 2 mmol / g.

83. The coated substrate of claim 20, wherein the feathering reducer (vi) comprising an oxazolyl functional group has a Tg > 30°C.

84. The coated substrate of claim 20, wherein the feathering reducer (vi) comprising an oxazolyl functional group has a Mn > 10,000 Da.

85. The coated substrate of claim 20, wherein the feathering reducing agent (vi) comprising an oxazolyl functional group is a polyoxazoline.

86. The coated substrate of claim 20, wherein the feathering reducer comprising an oxazolyl functional group (vi) is an acrylic feathering reducer comprising an oxazolyl functional group.

87. The coated substrate of claim 20, wherein the composition comprises a feathering reducing agent (vi) comprising an oxazolyl functional group in an amount ≥ 1% by weight of the solids of the coating composition.

88. The coated substrate of claim 20, wherein the composition comprises a feathering reducing agent (vi) comprising an oxazolyl functional group in an amount of ≤ 40% by weight of the solids of the coating composition.

89. The coated substrate of claim 1, wherein the feathering reducer reduces feathering in a coating formed from the coating composition comprising the feathering reducer as compared to the same composition without the feathering reducer as measured by Test Protocol 1.

90. The coated substrate of claim 1, wherein the feathering reducer reduces feathering in a coating formed from the coating composition comprising the feathering reducer by at least 20% as measured by Test Protocol 1, compared to the same composition without the feathering reducer.

91. The coated substrate of claim 1, wherein the coated substrate has a wedge bend of ≤ 30 mm.

92. The coated substrate of claim 1, wherein the coated substrate has a blush ≥ 4.

93. The coated substrate of claim 1, wherein the coated substrate has an adhesion of ≥ 90.

94. The coated substrate of claim 1, wherein the composition comprises an epoxy resin.

95. The coated substrate of claim 1, wherein the composition comprises a polyester additive that is the reaction product of a reaction mixture comprising (i) a polyacid, (ii) a polyol, and (iii) phosphoric acid.

96. The coated substrate of claim 1, wherein the composition comprises a cross-linked material.

97. The coated substrate of claim 1, wherein the substrate is formed from aluminum, tinplate, or tin-free steel (TFS).

98. The coated substrate of claim 1, wherein the substrate is a beverage package.

99. The coated substrate of claim 1, wherein the substrate is a metal can.

100. The coated substrate of claim 1, wherein the coating composition, the pretreatment composition, and / or layers deposited therefrom are substantially free, substantially free, or completely free of hexavalent chromium compounds.

101. The coated substrate of any one of claims 1-100, wherein the substrate comprises a packaging container.

102. The coated substrate of claim 101, wherein the packaging container comprises a metal can.

103. The coated substrate of claim 102, wherein when the coated tab portion of the metal can is removed or separated from the remainder of the metal can, the metal can has a feathering of ≤ 0.8 mm.

104. The coated substrate of claim 103, wherein the metal can is a beverage can.

105. A method of forming the coated substrate of any one of claims 1-104, the method comprising: a. contacting at least a portion of the substrate with the coating composition; and b. curing the coating composition to form a coating extending over at least a portion of the substrate.

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