Products coated with waterborne or powder coating compositions comprising acrylic polyester resins

Abstract

Disclosed are products having a coating applied to at least a portion thereof. The products can be vehicle products, home or office appliances, furniture or tooling, power industry products, consumer electronics, construction products, or products protected by an intumescent coating. The coating can be derived from a waterborne coating composition or a powder coating composition and can include an acrylic polyester resin obtainable by grafting an acrylic polymer with a polyester material obtainable by polymerizing a polyacid component with a polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol. Also disclosed are methods of application and uses.

Description

[0001] This application is a divisional application of Chinese patent application No. 201980062528.2.

[0002] This invention relates to a product having a coating on at least a portion thereof, said coating being derived from a water-based or powder coating composition. The product may be part of a vehicle, household appliance, power industry product, construction product, or article having an expanding coating. The invention also relates to a method of coating such a product and the use of a defined acrylic polyester resin composition in coating such products.

[0003] A wide variety of coatings have been used to coat many different types of products. Coating systems typically possess certain properties, such as the ability to be applied at high speeds, acceptable adhesion to the substrate, safety during or after application, and suitability for their end use. Generally, coatings possess one or more of these advantageous properties, depending on their final application.

[0004] Many traditional coating compositions are provided in volatile solvent carriers. However, there is now a desire to provide more environmentally friendly coating compositions that do not use volatile solvents or use less of the previously used volatile solvents. Water is a potential non-volatile solvent with a very small environmental impact. However, polyester materials that have historically been used in solvent carriers often have insufficient solubility in water. In cases where it is possible to use aqueous compositions to coat polyester materials onto substrates, the coating properties (e.g., rheology) are not always acceptable, and the resulting polyester coatings may have poor in-service properties (e.g., adhesion, lifespan, or durability).

[0005] The object of this invention is to provide a product as defined herein, which at least partially overcomes the problems previously encountered.

[0006] According to the present invention, a product having at least a portion thereof coated with a coating is provided, said product being a vehicle product, household or office appliance, furniture or tool, power industry product, consumer electronics, building product, or product protected by an intumescent coating, said coating being derived from a water-based coating composition or a powder coating composition, said coating composition comprising:

[0007] (a) An acrylic polyester resin, which can be obtained by grafting an acrylic polymer with a polyester material, said polyester material being obtained by polymerizing the following:

[0008] i) Polybasic acid components, and

[0009] ii) A polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol

[0010] The polyacid component or one of the polyol components includes a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0011] (b) Crosslinked materials.

[0012] According to the present invention, a method is provided for coating at least a portion of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating, the method comprising applying a coating composition to at least a portion of the surface of the product, the coating composition comprising an aqueous coating composition or a powder coating composition, the coating composition comprising an acrylic-modified polyester resin and a crosslinking material, the acrylic-modified polyester resin being obtained by grafting an acrylic polymer onto a polyester material, the polyester material being obtained by polymerizing the following:

[0013] i) Polybasic acid components, and

[0014] ii) A polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol

[0015] The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0016] And to cure the aqueous or powder composition to form a coating.

[0017] According to the present invention, there is a use of a coating composition comprising an aqueous composition or powder composition containing an acrylic-modified polyester resin and a crosslinking material, wherein the acrylic-modified polyester resin can be obtained by grafting an acrylic polymer onto a polyester material, and the polyester material can be obtained by polymerizing the following:

[0018] i) Polybasic acid components, and

[0019] ii) A polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol

[0020] The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0021] The coating composition is used to coat at least a portion of the surface of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating.

[0022] Advantageously, the inclusion of a polyol component, as defined, in polyester materials has been found to improve the hydrolytic stability of waterborne or powder coating compositions, thereby extending the lifespan of the polyester and the waterborne or powder coating composition. Similarly, the resistance properties of coatings derived from waterborne or powder coating compositions have also been found to be improved by the inclusion of the defined polyol component in the polyester material. Furthermore, the inclusion of the defined polyol component in the polyester material results in a better solids-to-viscosity ratio in the waterborne dispersion.

[0023] Acrylic polyester resins include acrylic-modified polyester resins, which can be polyester materials grafted with acrylic polymers. Acrylic-modified polyester resins can be prepared by grafting acrylic polymers onto pre-formed polyester materials. Acrylic-modified polyester resins can also be prepared by grafting a mixture of acrylic monomers onto a pre-formed polyester material.

[0024] The polyacid or polyol component includes functional monomers operable to impart functionality to the polyester resin. The functionality is such that the acrylic polymer can be grafted onto the polyester material using said functionality. The functionality may include olefinic unsaturation, carboxylic acid functionality, or epoxy functionality. The functionality may be in the main chain of the polyester material or in the resulting side chains (pendants).

[0025] Functional monomers may include olefinically unsaturated monomers operable to impart olefinically unsaturated functionality to the main chain or derived side chains of a polyester resin. Functionality may include olefinically unsaturation, which may be present in the main chain of the polyester material.

[0026] Suitable functional monomers may include the following: maleic acid; maleic anhydride; fumaric acid; itaconic anhydride; itaconic acid; citraconic anhydride; citraconic acid; aconitic acid; aconitic anhydride; oxalocitraconic acid; oxalocitraconic anhydride; mesoconic acid; mesoconic anhydride; phenylmaleic acid; phenylmaleic anhydride; tert-butylmaleic acid; tert-butylmaleic anhydride; monomethyl fumarate; monobutyl fumarate; nadic acid; nadic anhydride; methylmaleic acid; and / or methylmaleic anhydride.

[0027] The functional monomer is a polybasic acid, which may exist in an amount of 0.5 wt% to 10 wt% as a percentage of the dry weight of the polybasic acid component, and may exist in an amount of 1 wt% to 5 wt%.

[0028] The functional monomer is a polyol, which may exist as part of the dry weight of the polyol component in an amount of 0.5 wt% to 10 wt%, and may exist in an amount of 1 wt% to 5 wt%.

[0029] Polybasic acid components may include polybasic acids. As used herein, “polybasic acid” and similar terms refer to compounds having two or more carboxylic acid groups, such as two (diacid), three (tricid), or four acid groups, and comprising polybasic esters (where one or more acid groups in each acid group are esterified) or acid anhydrides. Polybasic acids may be organic polybasic acids.

[0030] The carboxylic acid groups of polyacids can be linked by bridging groups, which can be: alkylene; alkenylene; ynylene; or arylene.

[0031] Polyester materials can be formed from any suitable polybasic acid. Examples of suitable polybasic acids include, but are not limited to, the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanoic acid; dodecanoic 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; methyl hexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorobenzyl anhydride; 1,3-cyclohexane dicarboxylic acid; 1,4-cyclohexane dicarboxylic acid; tricyclodecane polycarboxylic acid; inner methylene tetrahydrophthalic acid; bridged ethylhexahydrophthalic acid; cyclohexane tetracarboxylic acid; cyclobutane tetracarboxylic acid; esters and anhydrides of all the foregoing acids and combinations thereof.

[0032] Polybasic acid components may include diacids. Examples of suitable 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-naphthalenedicarboxylic acid; n-phthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; diester materials, such as dimethyl ester derivatives (e.g., dimethyl isophthalate); dimethyl terephthalate; dimethyl 1,4-cyclohexanedicarboxylic acid; dimethyl 2,6-naphthalenedicarboxylic acid; dimethyl fumarate; dimethyl n-phthalate; dimethyl succinate; dimethyl glutarate; dimethyl adipate; esters and anhydrides of all the aforementioned acids; and mixtures thereof.

[0033] The polybasic acid components may include: terephthalic acid (TPA); isophthalic acid (IPA); dimethyl isophthalic acid; 1,4-cyclohexanedicarboxylic acid; hexahydrophthalic anhydride; 2,6-naphthalenedicarboxylic acid; phthalic anhydride; maleic anhydride; and / or fumaric anhydride.

[0034] The polybasic acid component may include: dimethyl terephthalate; hexahydrophthalic anhydride; and / or cyclohexane-1,4-dicarboxylic acid.

[0035] The polyol component includes polyols. As used herein, "polyol" and similar terms refer to compounds having two or more hydroxyl groups (e.g., two (diol), three (triol), or four hydroxyl groups). The hydroxyl groups of a polyol may be linked by bridging groups, which may be: alkylene; alkenylene; ynylene; or arylene. Polyols may be organic polyols.

[0036] In addition to the polyol components defined in this invention, polyester materials can 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; hexanediol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycols comprising 1,2-propanediol; 1,3-propanediol; butyl ethyl propylene glycol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; and propylene glycols comprising 1,4-butanediol; 1,3-butanediol; and Butanediols of 2-ethyl-1,4-butanediol; pentanediols comprising trimethylpentanediol and 2-methylpentanediol; cyclohexanediol; hexanediols comprising 1,6-hexanediol; caprolactone diols (e.g., the reaction product of ε-caprolactone and ethylene glycol); hydroxyalkylated bisphenols; polyether diols, such as poly(oxytetramethylene)diol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; dimethylolcyclohexane; glycerol, etc., or combinations thereof.

[0037] The polyol component may include diols. The polyol component may include any suitable diol. Examples of suitable diols include, but are not limited to, the following: ethylene glycol; 1,2-propanediol; 1,3-propanediol; 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; diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 2,2,4-trimethylpentane 1,3-diol; 1,4-cyclohexanediol; tricyclodecanediol; isosorbide; 1,4-cyclohexanediol; 1,1'-isopropylidene-bis(4-cyclohexanol); and mixtures thereof.

[0038] Specifically, the polyol component may include: 2-methylpropanediol (2-MPD); neopentyl glycol (NPG); 1,4-cyclohexanediol (CHDM); butyl ethyl propylene glycol (BEPD); trimethylolpropane (TMP) and / or 1,6-hexanediol.

[0039] The polyol compounds defined in this invention may be present in an amount of 10 wt% to 80 wt% as a percentage of the dry weight of the polyol component, and may be present in an amount of 10 wt% to 70 wt%.

[0040] The polyol component may include polyol compounds as defined in this invention in combination with 2-methyl-1,3-propanediol and / or cyclohexanediol.

[0041] 2,2,4,4-Tetraalkylcyclobutane-1,3-diol (TACD) is a polyol compound that can be used in this invention and can be represented by a general structure:

[0042]

[0043] R1, R2, R3, and R4 each independently represent an alkyl group, for example, having the following lower alkyl groups: 1 to 8 carbon atoms; or 1 to 6 carbon atoms; or 1 to 5 carbon atoms; or 1 to 4 carbon atoms; or 1 to 3 carbon atoms; or 1 to 2 carbon atoms; or 1 carbon atom. The alkyl group can be linear, branched, or a combination of linear and branched alkyl groups. Examples of TACDs include 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD); 2,2,4,4-tetraethylcyclobutane-1,3-diol (TECD); 2,2,4,4-tetra-n-propylcyclobutane-1,3-diol; 2,2,4,4-tetra-n-butylcyclobutane-1,3-diol; 2,2,4,4-tetra-n-pentylcyclobutane-1,3-diol; 2,2,4,4-tetra-n-hexylcyclobutane-1,3-diol; 2,2,4,4-tetra-n-heptylcyclobutane-1,3-diol; and 2,2,4,4-tetra-n-octylcyclobutane. -1,3-diol; 2,2-dimethyl-4,4-diethylcyclobutane-1,3-diol; 2-ethyl-2,4,4-trimethylcyclobutane-1,3-diol; 2,4-dimethyl-2,4-diethyl-cyclobutane-1,3-diol; 2,4-dimethyl-2,4-di-n-propylcyclobutane-1,3-diol; 2,4-n-dibutyl-2,4-diethylcyclobutane-1,3-diol; 2,4-dimethyl-2,4-diisobutylcyclobutane-1,3-diol; and 2,4-dimethyl-2,4-diisopentylcyclobutane-1,3-diol. Suitably, TACD includes 2,2,4,4-tetramethylcyclobutane-1,3-diol (“TMCD”).

[0044] Suitablely, the polyacid component and / or polyol component includes sulfonated monomers. Sulfonated monomers may include sulfonated diacids, such as sulfonated aromatic diacids. Sulfonated monomers may include their salts, such as inorganic salts, like metal salts or ammonium salts. Examples of metal salts will include, for example, sodium salts, lithium salts, potassium salts, magnesium salts, calcium salts, iron salts, etc.

[0045] The polyacid component may include sulfonated monomers.

[0046] The sulfonated monomer may include a metal salt of 5-(sulfonyl)-isophthalic acid, such as its sodium salt, which is referred to as 5-(sodium sulfonate)-isophthalic acid, and is also referred to herein as 5-SSIPA.

[0047] The 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.

[0048] The sulfonated monomers include polybasic acids, and the sulfonated monomers may exist in an amount of 5 wt% to 20 wt% (e.g., 7 wt% to 15 wt%) as a percentage of the dry weight of the polybasic acid component.

[0049] The sulfonated monomers include polyols, and the sulfonated monomers may exist in an amount of 5 wt% to 20 wt% (e.g., 7 wt% to 15 wt%) as a percentage of the dry weight of the polyol component.

[0050] The polyacid components may include: dimethyl terephthalate; isophthalic acid; hexahydrophthalic anhydride; cyclohexane-1,4-dicarboxylic acid; and / or 5-(sodium sulfonate)-isophthalic acid.

[0051] Functional monomers may include maleic acid, maleic anhydride and / or fumaric acid.

[0052] Polyester materials can be modified using acrylic acid compounds by grafting acrylic acid-modified polymers onto them. This grafting can occur through free radical polymerization, such as through free radical polymerization of olefinic unsaturated polymers onto polyester materials.

[0053] Acrylic-modified polymers can be the acrylic monomers formed. Acrylic-modified polymers can be grafted onto polyesters by polymerizing acrylic monomers in the presence of polyester materials to form acrylic-modified polyester resins.

[0054] Various acrylic monomers can be combined to prepare acrylic-modified polymers. Examples include methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; isobornyl (meth)acrylate; hydroxyethyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; (meth)acrylic acid; and nitrile monomers such as (meth)acrylonitrile. Any other acrylic monomers known to those skilled in the art may also be used. The term "(meth)acrylate" and similar terms are used conventionally and herein refer to both methacrylates and acrylates. Suitable acrylic-modified polymers are formed from: 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 (such as ethylene glycol methacrylate).

[0055] Acrylic-modified polymers may also include a certain amount (0 w% to 30 w% by dry weight of the acrylic-modified polymer) of non-acrylic monomers. These non-acrylic monomers may include other olefinically unsaturated monomers, such as styrene, ethylene, propylene, vinyltoluene, butadiene, 1-octene or isoprene, and vinyl esters (such as vinyl acetate).

[0056] It has been determined that acrylic-modified polymers may contain methacrylic acid or acrylic acid to impart acid functionality to the acrylic-modified polymers. The acid functionality on the acrylic-modified polymers can be at least partially neutralized with a neutralizing agent.

[0057] Useful neutralizing agents contain ammonia or amine functional groups: methylethanolamine, dimethylethanolamine (DMEA), trimethylamine, and diethylenetriamine.

[0058] The acid functionality of acrylic-modified polymers can be neutralized by at least 50% with a neutralizing agent. The acid functionality of acrylic-modified polymers can be neutralized by at least 75% with a neutralizing agent. The acid functionality of acrylic-modified polymers can be neutralized by at least 90% with a neutralizing agent.

[0059] The polyester material in acrylic-modified polyester resin includes sulfonated monomers, so neutralization of the acrylic-modified polyester resin is not required.

[0060] Polyester materials can have any suitable number-average molecular weight (Mn). The Mn of polyester materials can be from 1,000 Daltons (Da = g / mol) to 15,000 Da, for example 2,000 Da to 10,000 Da, such as 3,000 Da to 8,000 Da, or even 4,000 Da to 7,000 Da.

[0061] Number-average molecular weight can be measured by any suitable method. Techniques for measuring number-average molecular weight are well known to those skilled in the art. As reported herein, Mn can be determined by gel permeation chromatography according to the polystyrene standard of ASTM D6579-11 ("Standard Operating Procedure for Determination of Mean Molecular Weight and Molecular Weight Distribution of Hydrocarbon Resins, Rosin Resins and Terpene Resins by Size Exclusion Chromatography"; UV detector; 254 nm, solvent: unstable THF, retention time marker: toluene, sample concentration: 2 mg / ml).

[0062] Polyester materials can have any suitable glass transition temperature (Tg). The Tg of polyester materials can range from 0°C to 100°C.

[0063] Polyester materials can have any suitable total hydroxyl value (OHV). The total OHV of polyester materials can be from 0 mg KOH / g to 120 mg KOH / g. Suitablely, the total OHV of polyester materials can be from 5 mg KOH / g to 100 mg KOH / g, such as from 10 mg KOH / g to 60 mg KOH / g or even from 20 mg KOH / g to 40 mg KOH / g.

[0064] Where appropriate, total OHV is expressed in solid form.

[0065] Polyester materials can have any suitable acid value (AV). The AV of polyester materials can range from 0 KOH / g to 20 KOH / g. The total AV of polyester can range from 0 mg KOH / g to 10 mg KOH / g, for example, less than 5 or even less than 3.

[0066] Appropriately, AV is represented in solid form.

[0067] Acrylic polyester resins, which can be acrylic-modified polyester resins, can be present in coating compositions in an amount of 50 wt% to 99 wt% (based on the dry weight of the coating composition). Suitably, acrylic polyester resins, which can be acrylic-modified polyester resins, can be present in water-based or powder coating compositions in an amount of 60 wt% to 95 wt% (based on the dry weight of the water-based or powder coating composition).

[0068] Acrylic polyester resins that can be modified with acrylic resins can have any suitable number-average molecular weight (Mn). The Mn of acrylic polyester resins that can be modified with acrylic resins can be from 1,000 Daltons (Da = g / mol) to 15,000 Da, for example from 2,000 Da to 10,000 Da, such as from 3,000 Da to 8,000 Da, or even from 4,000 Da to 7,000 Da.

[0069] Number-average molecular weight can be measured by any suitable method. Techniques for measuring number-average molecular weight are well known to those skilled in the art. Suitablely, and as reported herein, Mn can be determined by gel permeation chromatography according to the polystyrene standard of ASTM D6579-11 (“Standard Operating Procedure for Determination of Mean Molecular Weight and Molecular Weight Distribution of Hydrocarbon Resins, Rosin Resins and Terpene Resins by Size Exclusion Chromatography”. UV detector; 254 nm, solvent: unstable THF, retention time marker: toluene, sample concentration: 2 mg / ml).

[0070] The Tg of acrylic modified polymers (a measure of the Tg of acrylic modified polymers when polymerized into simple acrylic polymers, not in the presence of polyester materials (or grafted onto polyester materials)) is 20°C to 120°C.

[0071] Acrylic polyester resins can have any suitable glass transition temperature (Tg) during curing. The Tg of acrylic polyester resins and / or coatings can range from 25°C to 200°C.

[0072] Cured coatings formed from coating compositions can have any suitable glass transition temperature (Tg). The Tg of a coating can range from 25°C to 200°C.

[0073] The Tg of the polyester material, the cured acrylic polyester resin and / or the cured coating derived from the coating composition may be at least 25°C, or at least 30°C, or at least 35°C, such as at least 40°C or at least 45°C, or at least 50°C, such as at least 55°C or at least 60°C, or at least 65°C, or at least 70°C, or at least 75°C or at least 80°C.

[0074] The Tg of the polyester material, acrylic polyester resin and / or coating formed by the coating composition can be up to 200°C, such as up to 150°C, or up to 120°C, or up to 110°C or up to 105°C.

[0075] The glass transition temperature (Tg) of polyester materials, acrylic polyester resins, and / or coatings can be measured by any suitable method. Methods for measuring Tg are well known to those skilled in the art. As reported herein, Tg can be measured according to ASTM D6604-00 (2013) (“Standard Practice for Glass Transition Temperatures of Hydrocarbon Resins by Differential Scanning Calorimetry”, differential scanning calorimetry (DSC), sample pan: aluminum, reference: blank, calibration: indium and mercury, sample weight: 10 mg, heating rate: 20 °C / min).

[0076] Acrylic-modified polyester resins can have any suitable total hydroxyl value (OHV). The total OHV of acrylic-modified polyester resins can range from 0 mg KOH / g to 120 mg KOH / g. The total OHV of acrylic-modified polyester resins can range from 5 mg KOH / g to 100 mg KOH / g, such as 10 mg KOH / g to 60 mg KOH / g, or even 20 mg KOH / g to 50 mg KOH / g.

[0077] Where appropriate, total OHV is expressed in solid form.

[0078] Acrylic-modified polyester resins can have any suitable acid value (AV). The AV of acrylic-modified polyester resins can be from 10 KOH / g to 80 KOH / g. The total AV of acrylic-modified polyester resins can be from 20 mg KOH / g to 70 mg KOH / g, such as from 30 mg KOH / g to 60 mg KOH / g.

[0079] Appropriately, AV is represented in solid form.

[0080] Suitablely, the acrylic-modified polyester resin can be formed from polyester material and acrylic-modified polymer in a weight ratio of 85 wt% to 55 wt% polyester material to 45 wt% to 15 wt% acrylic-modified polymer, such as 80 wt% to 60 wt% polyester material to 40 wt% to 20 wt% acrylic-modified polymer, such as 75 wt% to 65 wt% polyester material to 35 wt% to 25 wt% acrylic-modified polymer. For example, the acrylic-modified polyester resin can be formed from polyester material and acrylic-modified polymer in a weight ratio of 70 wt% polyester material to 30 wt% acrylic-modified polymer.

[0081] Acrylic polyester resins, which can be acrylic-modified polyester resins, can be present in aqueous or powder coating compositions in an amount of 50 wt% to 99 wt% (based on the dry weight of the aqueous or powder coating composition). Suitably, acrylic polyester resins can be present in aqueous or powder coating compositions in an amount of 60 wt% to 95 wt% (based on the dry weight of the aqueous or powder coating composition).

[0082] The polyester material according to the invention can be prepared in the presence of an esterification catalyst. Suitably, the esterification catalyst can be selected to promote the esterification reaction and / or transesterification reaction of the components. Examples of suitable esterification catalysts for use in the preparation of the polyester material include, but are not limited to, the following: metal compounds, such as stannous octanoate; stannous chloride; butyl stannous acid (hydroxybutyl tin oxide); monobutyltin tri(2-hexanoate); 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); tetraalkylzirconium materials; antimony trioxide; germanium dioxide; bismuth octanoate; and combinations thereof. The esterification catalyst may be dodecylbenzenesulfonic acid (DDBSA).

[0083] The esterification catalyst (if present) may be used in an amount of 0.001% to 1% of the total polymer component by weight, suitably 0.01% to 0.2% (e.g., 0.025% to 0.2%) of the total polymer component by weight.

[0084] Unless otherwise defined, the term "alk or alkyl" as used herein refers to a saturated hydrocarbon group comprising a straight-chain, branched, cyclic, or polycyclic moiety or a combination thereof and containing 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or even 1 to 4 carbon atoms. These groups may optionally be oxidized by chlorine, bromine, iodine, cyano, nitro, or OR. 19 OC(O)R 20 C(O)R 21 C(O)OR22 NR 23 R 24 C(O)NR 25 R 26 SR 27 C(O)SR 27 C(S)NR 25 R 26 aryl or heteroatom substitution (where R 19 To R 27 Each group (independently representing hydrogen, aryl, or alkyl) and / or interrupted by an oxygen or sulfur atom or by a silane or dialkylsiloxane group. Examples of such groups can be independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, pentyl, isopentyl, hexyl, cyclohexyl, 3-methylpentyl, octyl, etc. As used herein, the term "alkylene" refers to a divalent alkyl group as defined above. For example, an alkyl group such as methyl, which would be represented as –CH3, becomes methylene –CH2- when represented as alkylene. Other alkylene groups should be understood accordingly.

[0085] As used herein, the term "alkenyl" refers to a hydrocarbon group comprising a straight-chain, branched, cyclic, or polycyclic moiety or a combination thereof, and containing 2 to 18 carbon atoms, suitably 2 to 10 carbon atoms, more suitably 2 to 8 carbon atoms, still more suitably 2 to 6 carbon atoms, and even more suitably 2 to 4 carbon atoms, having a double bond (suitably up to 4 double bonds). These groups may optionally be derived from hydroxyl, chlorine, bromine, iodine, cyano, nitro, or OR groups. 19 OC(O)R 20 C(O)R 21 C(O)OR 22 NR 23 R 24 C(O)NR 25 R 26 SR 27 C(O)SR 27 C(S)NR 25 R 26 Or aryl substitution (where R) 19 To R 27Each group (independently representing hydrogen, aryl, or alkyl) and / or interrupted by an oxygen or sulfur atom or by a silane or dialkylsiloxane. Examples of such groups can be alkenyl groups, including vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, isopryl, farnesyl, geranyl, geranylgeranyl, etc. As used herein, the term "alkenyl" refers to a divalent alkenyl group as defined above. For example, an alkenyl group such as a vinyl group that would be represented as –CH=CH2 becomes vinylene-CH=CH- when represented as an alkenyl group. Other alkenyl groups should be understood accordingly.

[0086] As used herein, the term "alkynyl" refers to a hydrocarbon group having a straight-chain, branched, cyclic, or polycyclic moiety or a combination thereof, and having 2 to 18 carbon atoms, suitably 2 to 10 carbon atoms, more suitably 2 to 8 carbon atoms, still more suitably 2 to 6 carbon atoms, and even more suitably 2 to 4 carbon atoms, and having a triple bond (suitably up to 4 triple bonds). These groups may optionally be derived from hydroxyl, chlorine, bromine, iodine, cyano, nitro, or OR groups. 19 OC(O)R 20 C(O)R 21 C(O)OR 22 NR 23 R 24 C(O)NR 25 R 26 SR 27 C(O)SR 27 C(S)NR 25 R 26 Or aryl substitution (where R) 19 To R 27 Each group (independently representing hydrogen, aryl, or lower alkyl) and / or interrupted by an oxygen or sulfur atom or by a silane or dialkylsiloxane. Examples of such groups can be independently ynyl groups, including ethynyl, propynyl, propynyl, butynyl, pentyynyl, hexynyl, etc. As used herein, the term "ynynyl" refers to a divalent ynyl group as defined above. For example, an ynyl group such as ethynyl, which would be represented as –C≡CH, becomes ethynyl-C≡C- when represented as an ynynyl. Other ynynyl groups should be understood accordingly.

[0087] As used herein, the term "aryl" refers to an organic group derived from an aromatic hydrocarbon with one hydrogen atom removed, and comprising any monocyclic, bicyclic, or polycyclic carbon ring having up to seven members per ring, wherein at least one ring is aromatic. These groups may optionally be hydroxyl, chlorine, bromine, iodine, cyano, nitro, or OR 19 OC(O)R 20 C(O)R 21C(O)OR 22 NR 23 R 24 C(O)NR 25 R 26 SR 27 C(O)SR 27 C(S)NR 25 R 26 Or aryl substitution (where R) 19 To R 27 Each of these groups independently represents hydrogen, aryl, or lower alkyl groups and / or is interrupted by an oxygen atom or a sulfur atom or by a silane or dialkylsilyl group. Examples of such groups can be independently phenyl, p-tolyl, 4-methoxyphenyl, 4-(tert-butoxy)phenyl, 3-methyl-4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 3-aminophenyl, 3-acetaminophenyl, 4-acetaminophenyl, 2-methyl-3-acetaminophenyl, 2-methyl-3-aminophenyl, 3-methyl-4-aminophenyl, 2-amino-3-methylphenyl, 2,4-dimethyl-3-aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1-naphthyl, 2-naphthyl, 3-amino-1-naphthyl, 2-methyl-3-amino-1-naphthyl, 6-amino-2-naphthyl, 4,6-dimethoxy-2-naphthyl, tetrahydronaphthyl, indanyl, biphenyl, phenanthryl, anthraceneyl, or acenaphthyl, etc. As used herein, the term "aryl" refers to the divalent aryl group as defined above. For example, aryl groups such as phenyl groups that would be represented as –Ph become phenylene –Ph- when represented as arylene groups. Other arylene groups should be understood accordingly.

[0088] To avoid ambiguity, references to alkyl, alkenyl, alkynyl, aryl, or aralkyl groups in this document should be interpreted accordingly. For example, references to alkyl groups in aminoalkyl groups or alkyl groups in alkoxy groups should be interpreted as alkyl groups (alk or alkyl) as described above.

[0089] The water-based and powder coating compositions of the present invention include a crosslinking material. The crosslinking material is operable to crosslink an acrylic-modified polyester resin. The crosslinking material can be a monomer, dimer, oligomer, (co)polymer, or mixture thereof. The crosslinking material can be a dimer or trimer.

[0090] The crosslinking material can be manipulated to crosslink acrylic polyester resin.

[0091] Crosslinking materials may include any suitable crosslinking materials. Suitable crosslinking materials are well known to those skilled in the art. Suitable crosslinking materials include, but are not limited to, the following: benzomelamine, phenolic resin (or phenol-formaldehyde resin); amino plastic resin (or triazine-formaldehyde resin); amino resin; epoxy resin; isocyanate resin; β-hydroxy(alkyl)amide resin; alkylated urethane resin; polybasic acid; acid anhydride; organometallic acid functional materials; polyamine; polyamide and combinations thereof.

[0092] Non-limiting examples of phenolic resins are those formed by reacting phenol with an aldehyde or ketone, suitably 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", Volume V, Part I, edited by Dr. Oldring; John Wiley and Sons / Cita Technology Limited, London, 1997. Suitably, phenolic resins belong to the alpha-phenolic resin type. "Alkaline phenolic resin type" means resins formed in the presence of an alkaline catalyst and optionally in excess formaldehyde. Suitable examples of commercially available phenolic resins include, but are not limited to, the following: phenolic resins sold under the trade name PHENODUR (RTM) from Cytec Industries, such as PHENODUR EK-827, PHENODUR VPR1785, PHENODURPR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODUR PR612, or PHENODUR PH2024; resins sold under the trade name BAKELITE (RTM) from Momentive, such as BAKELITE 6582 LB, BAKELITE 6535, BAKELITE PF9989, or BAKELITE PF6581; SFC 112 from Schenectady; and DUREZ from SHHPP. (RTM)33356; ARALINK (RTM) 40-852, available from Bitrez; or a combination thereof.

[0093] Waterborne or powder coating compositions may be substantially formaldehyde-free, suitably substantially formaldehyde-free, or suitably completely formaldehyde-free. "Substantially formaldehyde-free" means a waterborne or powder coating composition containing less than 1,000 parts per million (ppm) of any of the above-mentioned compounds or their derivatives. "Substantially formaldehyde-free" means a waterborne or powder coating composition containing less than 100 ppm of any of the above-mentioned compounds or their derivatives. "Completely formaldehyde-free" means a waterborne or powder coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or their derivatives.

[0094] Non-limiting examples of isocyanate resins include, but are not limited to, the following: isophorone diisocyanates (IPDI), such as those resins available from Bayer under the trade name DESMODUR (RTM), e.g., DESMODURVP-LS 2078 / 2 or DESMODUR PL 340, or those resins available from Evonik under the trade name VESTANAT (RTM), e.g., VESTANANT B 1370, VESTANAT B 118 6A, or VESTANAT B 1358A; hexamethylene diisocyanate (HDI)-terminated aliphatic polyisocyanates, such as those resins available from Bayer under the trade name DESMODUR (RTM), e.g., DESMODUR BL3370 or DESMODUR BL 3175 SN; and those available from Asahi Kasei under the trade name DURANATE. Resins sold under the trade name TOLONATE (RTM), such as DURANATE MF-K60X; resins available from Perstorp under the trade name TOLONATE (RTM), such as TOLONATE D2; or resins available from Baxenden under the trade name TRIXENE (RTM), such as TRIXENE-BI-7984 or TRIXENE 7981; or combinations thereof.

[0095] Crosslinked materials may contain nitrogen. Crosslinked materials may be in the form of amines or amides. Crosslinked materials may include hydroxyl-substituted amines or amides.

[0096] Suitable crosslinking materials may include hydroxyalkylamide materials, such as β-hydroxyalkylamide materials.

[0097] Crosslinked materials may contain terminal chemical groups as shown in Formula I.

[0098]

[0099] Formula I

[0100] Where R 10 Indicates an electron-withdrawing group, such as (=O); and Y 1 and Y 2 Each can be used independently to represent a C1 to C3 alkylene group.

[0101] The terminal chemical group of Formula I can be attached to other chemical structures, not shown. Alternatively or alternatively, for example, the chemical group of Formula I can be suspended on a carrier substrate such as a silicon carrier substrate.

[0102] Crosslinked materials may contain multiple terminal chemical groups as shown in Formula I. For example, crosslinked materials may contain two, three, or four terminal chemical groups as shown in Formula I.

[0103] Crosslinked materials may include the portion according to Formula II:

[0104]

[0105] Formula II

[0106] Where R 10 and R 11 Each can independently represent an electron-withdrawing group, such as (=O); Y 1 Y 2 Y 3 and Y 4 Each of these characters independently represents a C1 to C3 alkylene group; and X represents a C2 to C6 alkylene group.

[0107] Appropriately, R 10 and R 11 Each of them represents an O group.

[0108] Appropriately, Y 1 Y 2 Y 3 and Y 4 Each of these represents vinyl.

[0109] Appropriately, X represents butenyl.

[0110] Accordingly, the crosslinking material may include the material of Formula III:

[0111]

[0112] Formula III

[0113] Crosslinking materials may include commercially available β-hydroxyalkylamide crosslinks, such as PRIMID XL-552 (available from Rohm and Haas); PRIMID QM-1260 (available from EMS Chemie); and N,N,N',N'-tetra(2-hydroxypropyl)hexamethylenediamine.

[0114] Crosslinked materials can be in the form of urea materials. Crosslinked materials can include hydroxyl-substituted urea materials.

[0115] Suitable crosslinking materials may include hydroxy-functionalized alkyl polyurea materials.

[0116] Crosslinked materials may contain terminal chemical groups as shown in Formula IV.

[0117]

[0118] Formula IV

[0119] Where Y 5 and Y 6 Each of these can independently represent hydrogen, an alkyl or hydroxyl-functionalized alkyl group having two or more carbon atoms, and Y 5 and Y 6 At least one of them is a hydroxy-functionalized alkyl group having two or more carbon atoms.

[0120] Y 5 and Y 6 The group can exclude ether bonds.

[0121] The terminal chemical group of Formula IV can be attached to other chemical structures, not shown. Alternatively or alternatively, for example, the chemical group of Formula IV can be suspended on a carrier substrate such as a silicon carrier substrate.

[0122] Crosslinked materials may contain multiple terminal chemical groups as shown in Formula IV. For example, crosslinked materials may contain 2 to 6 terminal chemical groups as shown in Formula IV, or 2, 3 or 4 terminal chemical groups as shown in Formula IV.

[0123] Crosslinked materials may include the portion according to formula V:

[0124]

[0125] Formula V

[0126] Wherein R includes residues of isocyanurate, biuret, urethane, glycourea, benzomelamine and / or polyetheramine; each R1 is independently hydrogen, an alkyl or hydroxy functional alkyl having two or more carbons, and at least one R1 is a hydroxy functional alkyl having two or more carbons; and n is 2 to 6.

[0127] Suitablely, the R1 group can exclude ether bonds.

[0128] Crosslinked materials may include the portion according to Formula VI:

[0129]

[0130] Style VI

[0131] R2 includes substituted or unsubstituted C1 to C2. 36 Alkyl, aromatic groups or residues of isocyanurate, biuret, urethane, glycourea, benzomelamine and / or polyetheramine; each R1 is independently hydrogen, an alkyl group having one or more carbons or a hydroxyfunctional alkyl group having two or more carbons, and at least one R1 is a hydroxyfunctional alkyl group having two or more carbons; and n is 2 to 6.

[0132] Suitablely, the R1 group can exclude ether bonds.

[0133] R and R2 may include residues of isocyanurates, biuret, urethane, glycourea, benzomelamine, and / or polyetheramines. Isocyanurates will be understood to refer to compounds having three isocyanate groups (usually in cyclic form) and are sometimes referred to as trimers. This can include compounds having an isocyanurate moiety. Isocyanurates are available from Covestro and Vencore X Chemical. Suitable commercially available isocyanurates include those sold under the trade name DESMODUR, such as DESMODUR N 3300A, DESMODUR N3800, DESMODUR N3400, DESMODUR N3600, DESMODUR N3900 and DESMODUR RC (available from Covestro); those sold under the trade name VESTANANT, such as VESTANATT1890 / 100 (available from Evonik); and those sold under the trade name EASAQUA, such as EASAQUA WT 2102, EASAQUA XD 401, EASAQUA M 501, EASAQUA XD 803, EASAQUA M 502 and EASAQUA XL 600 (available from Vencore X Chemicals). Particularly suitable hydroxy-functionalized alkyl polyureas formed from isocyanurates are shown in Formula VII:

[0134]

[0135] Equation VII

[0136] Wherein R1 is as described above; and each R3 independently comprises alkyl, aryl, alkylaryl, aralkyl, alicyclic and / or polyetheralkyl.

[0137] Particularly suitable hydroxy-functionalized alkyl polyureas formed from diisocyanurates are shown in the following formula VIII:

[0138]

[0139] Formula VIII

[0140] R1 and R3 are as described above.

[0141] Biuret will be understood to refer to compounds formed by the condensation of two urea molecules, and is sometimes called carbamoylurea. Biuret is commercially available from companies such as Vencore X Chemicals and Covestro, for example DESMODUR N-75, DESMODUR N-100 and DESMODUR N-3200, HDB 75B, HDB 75M, HDB 75MX, and HDB-LV. Particularly suitable hydroxyl-functionalized alkyl polyureas formed from biuret are shown in the following formula IX:

[0142]

[0143] Formula IX

[0144] Wherein R1 is as described above; each R5 independently comprises alkyl, aryl, alkylaryl, aralkyl, alicyclic and / or polyether alkyl; and R6 comprises H or alkyl.

[0145] Urea diketone is a dimer of a diisocyanate, examples of which include DESMODUR N-3400 polyisocyanate (a blend of a trimer and HDI urea diketone):

[0146]

[0147] Each R5 independently comprises alkyl, aryl, alkylaryl, aralkyl, alicyclic and / or polyether alkyl.

[0148] Urea carbamates will be understood to refer to compounds derived from urea and isocyanates. Methods for preparing urea carbamates are described in Surface Coating, Volume 1, Raw Material and Their Usage, Landon, New York, Chapman and Hall, page 106. The reaction is generally depicted in Scheme I below:

[0149]

[0150] Option I

[0151] R5 and R6 are each as described above; and R7 independently includes residues of a primary alcohol that reacts with isocyanate.

[0152] Glycourea will be understood to refer to compounds consisting of two cyclic urea groups linked across the same two-carbon chain, and suitable examples of glycourea include the following:

[0153]

[0154] Glycourea is widely available, such as from Sigma-Aldrich.

[0155] Benzyl melamine, also known as 6-phenyl-1,3,5-triazine-2,4-diamine, is available from The Chemical Company, Jamestown, RI.

[0156] Polyetheramines will be understood to refer to compounds having amine groups attached to the polyether backbone, such as those characterized by propylene oxide, ethylene oxide, or repeating units of propylene oxide and ethylene oxide mixed in their respective structures, as in one of the Jeffamine product families. Examples of such polyetheramines include amination-propoxylated pentaerythritol (such as JEFFAMINEXTJ-616) and those compounds represented by formulas (X) to (VI).

[0157] Polyetheramines according to formula (IV) may include:

[0158]

[0159] Formula X

[0160] Where y = 0-39, x+z = 1-68.

[0161] Suitable amine-containing compounds represented by formula X include, but are not limited to: amine-terminated polyethylene glycols, such as those commercially available from Huntsman Corporation's JEFFAMINE ED series, such as JEFFAMINE HK-511, JEFFAMINE ED-600, JEFFAMINE ED-900 and JEFFAMINE ED-2003; and amine-terminated polypropylene glycols, such as JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000 and JEFFAMINE D-4000, from its JEFFAMINE D series.

[0162] Polyetheramines according to formula XI may include:

[0163]

[0164] Formula XI

[0165] Each p is independently 2 or 3.

[0166] Suitable amine-containing compounds represented by formula XI include, but are not limited to, polyethylene glycol diamines with amine ends, such as Huntsman's JEFFAMINE EDR series, such as JEFFAMINE EDR-148 and JEFFAMINE EDR-176.

[0167] Polyetheramines according to formula XII may include:

[0168]

[0169] Formula XII

[0170] Where R8 is H or C2H5, m = 0 or 1, and a+b+c = 5-85.

[0171] Suitable amine-containing compounds represented by formula (VI) include, but are not limited to, propoxylated trimethylolpropane or glycerol with an amine terminus, such as Huntsman's Jeffamine T series, such as JEFFAMINE T-403, JEFFAMINE T-3000 and JEFFAMINE T-5000.

[0172] Diamines and triamines are particularly suitable, such as 4,7,10-trioxa-1,13-tridecanediamine, JEFFAMINE D400, JEFFAMINE D4000, JEFFAMINE D2000, and JEFFAMINE T403.

[0173] In all cases, R2 can be substituted or unsubstituted. As mentioned above, R2 can also include substituted or unsubstituted C1 to C2. 36 Alkyl and / or aromatic groups. For example, the alkyl group can have two to ten carbon atoms, such as six carbon atoms. The alkyl group can be derived from isocyanates, such as diisocyanates. Suitable examples include isophorone diisocyanate and hexamethylene isocyanate. The aromatic group can be derived from an aromatic ring containing an isocyanate, and suitable examples of said isocyanate include methylene biphenyl diisocyanate, toluene diisocyanate, and tetramethylphenyl diisocyanate.

[0174] Certain hydroxyfunctional alkyl polyureas of the present invention and / or used according to the present invention can be prepared by reacting isocyanate-containing compounds with amino alcohols. Any isocyanate-containing compound having at least two isocyanate groups can be used, such as any of the isocyanate-containing compounds described above. It will be understood that the “R” or “R2” group will reflect the isocyanate-containing compound used.

[0175] Similarly, any amino alcohol having two or more carbon atoms can be used, and the "R1" group will reflect the amino alcohol used. The amino alcohol can have one, two, or more hydroxyl functional groups. Amino alcohols can be used, which will result in different R1 groups appearing on the polyurea. R1 can also be hydrogen or alkyl. Suitable amino alcohols include monoethanolamine, diethanolamine, and diisopropylamine.

[0176] Hydroxyl-functionalized alkyl polyureas can be prepared by reacting amino alcohols with isocyanate-containing compounds in a polar organic solvent (such as alcohol or water). The reaction temperature can be maintained below 35°C. The equivalence ratio of amine to isocyanate can be 2-1:1-2, such as 1:1.

[0177] The hydroxyfunctional alkyl polyureas of the present invention and / or those used according to the present invention can also be prepared by alternative methods. For example, amino alcohols can react with carbonates to form hydroxyalkyl carbamates, and hydroxyalkyl carbamates can further react with amines to form hydroxyfunctional alkyl polyureas.

[0178] The number-average molecular weight (Mn) of hydroxyfunctional alkyl polyurea can be 100 or greater, such as 350 or greater or 1,000 or greater, and / or can be 6,000 or less, such as 3,000 or less or 2,000 or less. Mn refers to the theoretical value determined by gel permeation chromatography using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector) and a polystyrene standard. The molecular weight range of the polystyrene standard used in this method is approximately 800 g / mol to 900,000 g / mol. In determining Mn according to the invention, tetrahydrofuran (THF) is used as the eluent at a flow rate of 1 ml min⁻¹, and separation is performed using two PL gel-mixed C₂ columns.

[0179] Hydroxyl-functionalized alkyl polyurea materials can be prepared by reacting dialkylolamine with hexamethylene diisocyanate (HDI) trimers and / or isophorone diisocyanate (IDPI) trimers, preferably hexamethylene diisocyanate (HDI) trimers. Hydroxyl-functionalized alkyl polyurea materials can also be prepared by reacting diisopropanolamine with hexamethylene diisocyanate (HDI) trimers and / or isophorone diisocyanate (IDPI) trimers, preferably hexamethylene diisocyanate (HDI) trimers.

[0180] The crosslinking material that may be present in the aqueous or powder coating compositions of the present invention is any suitable amount. The aqueous or powder coating composition may include 0.5 wt% to 40 wt%, suitably 1 wt% to 30 wt% (e.g., 5 wt% to 20 wt%) of crosslinking material based on the total solid weight of the aqueous or powder coating composition.

[0181] Crosslinking materials may include phenolic resins, benzo-melamine and / or melamine.

[0182] Aqueous or powder coating compositions may include catalysts. Examples of suitable catalysts include, but are not limited to, the following: metal compounds such as stannous octanoate; stannous chloride; butyl stannous acid (hydroxybutyl tin oxide); monobutyltin tri(2-ethyl hexanoate); 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 terminally capped DDBSA), tetraalkylzirconium materials, antimony trioxide, germanium dioxide, bismuth octanoate, and combinations thereof. Catalysts may include dodecylbenzenesulfonic acid (DDBSA), such as terminally capped DDBSA.

[0183] The catalyst may be present in the aqueous or powder coating composition in an amount of 0.001% to 1% of the dry weight of the aqueous or powder coating composition, suitably in an amount of 0.01% to 0.7% (e.g., 0.025% to 0.5%) of the dry weight of the aqueous or powder coating composition.

[0184] The aqueous or powder coating compositions according to the present invention may be substantially free of bisphenol A (BPA) and its derivatives. The aqueous or powder coating compositions according to the present invention may be substantially free of or may be completely free of bisphenol A (BPA) and its derivatives. Bisphenol A derivatives include, for example, bisphenol A diglycidyl ether (BADGE).

[0185] The aqueous or powder coating compositions according to the present invention may be substantially free of bisphenol F (BPF) and its derivatives. The aqueous or powder coating compositions according to the present invention may be substantially free of or may be completely free of bisphenol F (BPF) and its derivatives. Derivatives of bisphenol F include, for example, bisphenol F diglycidyl ether (BPFG).

[0186] The aqueous or powder coating compositions according to the present invention may be substantially styrene-free. The aqueous or powder coating compositions according to the present invention may be substantially styrene-free or may be completely styrene-free.

[0187] The aforementioned compounds or their derivatives, namely BPA, BPF, and their derivatives, may be unintentionally added to the composition but may be present in trace amounts due to unavoidable environmental contamination. "Substantially free" means a coating composition containing less than 1000 parts per million (ppm) of any of the aforementioned compounds or their derivatives. "Substantially free" means a coating composition containing less than 100 ppm of any of the aforementioned compounds or their derivatives. "Completely free" means an aqueous or powder coating composition containing less than 20 parts per billion (ppb).

[0188] Water-based or powder coating compositions may include adhesion promoters. Adhesion promoters may include acidic polyesters.

[0189] Acidic polyesters may be added in amounts from 0.1 wt% to 15 wt% (based on the dry weight of the water-based or powder coating component), more preferably from 2 wt% to 12 wt% (based on the dry weight of the water-based or powder coating component). Acidic polyesters may be present in amounts from 4 wt% to 10 wt% (based on the dry weight of the water-based or powder coating component).

[0190] Acidic polyesters may include reaction products of polyesters with phosphorous acid (such as phosphoric acid). In this context, the Mn of the polyester can be from 2,000 to 10,000. The number of hydroxyl groups in the polyester can be from 20 to 75. The acid value of the polyester can be from 15 to 25.

[0191] Suitable acid polyesters comprise solutions of copolymers with acidic groups having an acid value ranging from 15 mg KOH / g to up to 100 mg KOH / g. Examples of commercially available suitable acid polyesters include BYK-4510 (available from Byk Altana), PLUSOLIT H-PD (available from Mäder), BORCHI GEN HMP-F, or BORCHI GEN HE (available from OMG Borchers).

[0192] Suitable, acid polyesters may typically include reaction products of the following substances:

[0193] (a) A polyester having an Mn of 2000 to 10,000, a hydroxyl number of 20 to 75, and an acid value of 15 to 25; said polyester being a condensation polymer of the following substances:

[0194] (i) Polyol components comprising a mixture of diols and triols,

[0195] (ii) Polyacid components including α,β-olefinically unsaturated polycarboxylic acids,

[0196] as well as

[0197] (b) Phosphorous acid.

[0198] Other suitable examples of acidic polyesters are given in WO 2012 / 162301, the contents of which are incorporated herein by reference in their entirety.

[0199] The aqueous or powder coating compositions of the present invention may include additional resin materials. Suitable additional resin materials are well known to those skilled in the art. Examples of suitable additional resin materials include, but are not limited to, the following: polyester resins; acrylic resins; polyvinyl chloride (PVC) resins; alkyd resins; polyurethane resins; polysiloxane resins; epoxy resins or combinations thereof. Suitably, the additional resin material may include polyvinyl chloride (PVC) resins.

[0200] The aqueous or powder coating compositions of the present invention may include other optional materials well known in the field of coating formulation, such as colorants, plasticizers, abrasion-resistant particles, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic cosolvents, reactive diluents, catalysts, abrasive mediators, lubricants, waxes, and other commonly used additives. The use of a certain amount of non-polymerizable surfactants in combination with polymerizable surfactants in the preparation of latexes and / or in coatings comprising latexes may be particularly desirable.

[0201] As used herein, the term "colorant" means any substance that imparts color and / or other opacity and / or other visual effects to a composition. Colorants can be added to aqueous or powder coatings in any suitable form, such as discrete particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used in the aqueous or powder coatings of the present invention. Suitable colorants are listed in U.S. Patent No. 8,614,286, column 7, line 2 through column 8, line 65, which is incorporated herein by reference. Those food-contact colorants are particularly suitable for packaging coatings, such as titanium dioxide; iron oxide, such as black iron oxide; aluminum paste; aluminum powder, such as aluminum flakes; carbon black; ultramarine; phthalocyanine, such as phthalocyanine blue and phthalocyanine green; chromium oxide, such as chromium oxide green; graphite fibers; ferry yellow; quindo red; and combinations thereof, as well as those colorants listed in Code of Federal Regulations 178.3297, which is incorporated herein by reference.

[0202] Waterborne or powder coating compositions may include aluminum paste, aluminum powder (such as aluminum flakes), or combinations thereof. Suitably, waterborne or powder coating compositions may include aluminum paste.

[0203] Colorants (when present) may be used in aqueous or powder coating compositions in any suitable amount. Colorants (when present) may be used in aqueous or powder coating compositions in amounts up to 90 wt% (e.g., up to 50 wt%) or even up to 10 wt% based on the total solid weight of the aqueous or powder coating composition.

[0204] Suitable lubricants are well known to those skilled in the art. Examples of suitable lubricants include, but are not limited to, carnauba wax, PTFE, polypropylene, and polyethylene lubricants. The lubricant (if present) may be used in the aqueous or powder coating composition in an amount of at least 0.01 wt%, suitably from 0.5 wt% to 2 wt%, based on the total solids weight of the aqueous or powder coating composition.

[0205] Surfactants may optionally be added to aqueous or powder coating compositions to aid in the flow and wetting of the substrate. Suitable surfactants are well known to those skilled in the art. Suitably, surfactants compatible with food and / or beverage container applications (when present) are selected. Suitable surfactants include, but are not limited to, the following: alkyl sulfates (e.g., sodium dodecyl sulfate); ether sulfates; phosphate esters; sulfonates; and various alkali salts, ammonium salts, and amine salts thereof; fatty alcohol ethoxylates; alkylphenol ethoxylates (e.g., nonylphenol polyether); salts and / or combinations thereof. The surfactant (when present) may be present in an amount of 0.01 wt% to 10 wt%, suitably 0.01 wt% to 5 wt% (e.g., 0.01 wt% to 2 wt%) based on the total solids weight of the aqueous or powder coating composition.

[0206] The water-based or powder coating compositions of the present invention may be substantially free of, substantially free of, or completely free of dialkyltin compounds, said dialkyltin compounds comprising their oxides or other derivatives. Examples of dialkyltin compounds include, but are not limited to, the following: dibutyltin dilaurate (DBTDL); dioctyltin dilaurate; dimethyltin oxide; diethyltin oxide; dipropyltin oxide; dibutyltin oxide (DBTO); dioctyltin oxide (DOTO); or combinations thereof. "Substantially free of" means a coating composition containing less than 1,000 parts per million (ppm) of any of the above-mentioned compounds or their derivatives. "Substantially free of" means a coating composition containing less than 100 ppm of any of the above-mentioned compounds or their derivatives. "Completely free of" means a coating composition containing less than 20 parts per billion (ppb) of any of the above-mentioned compounds or their derivatives.

[0207] The products of this invention can be vehicle products, household or office appliances, furniture or tools, power industrial products, consumer electronics, building products, or products protected by intumescent coatings.

[0208] Vehicle products can be vehicles or any components thereof. Any component or surface of a vehicle that may be coated to improve its properties (such as its gloss, scratch resistance, corrosion resistance, or UV resistance) may be a coating having a composition as defined herein.

[0209] The term "vehicle" is used in its broadest sense and includes (but is not limited to) all types of aircraft, spacecraft, watercraft, and land vehicles. For example, vehicles can include aircraft (such as airplanes, including private aircraft) as well as small, medium, or large commercial passenger aircraft, cargo aircraft, and military aircraft; helicopters, including private, commercial, and military helicopters; and aerospace vehicles, including rockets and other spacecraft. Vehicles can include land vehicles such as trailers, cars, trucks, buses, long-distance coaches, freight cars, ambulances, fire trucks, RVs, travel trailers, mini-cars, carriages, forklifts, sit-on lawnmowers, agricultural vehicles (e.g., tractors and harvesters), construction vehicles (e.g., excavators, bulldozers, and cranes), golf carts, motorcycles, bicycles, trains, and trams. Vehicles also include watercraft such as ships, submarines, small boats, jet skis, and hovercraft.

[0210] The vehicle components coated according to the present invention may include body components (e.g., but not limited to doors, body panels, trunk lids, roof panels, hoods, roofs and / or longitudinal struts, rivets, wheels, landing gear assemblies and / or shells used on aircraft), hulls, ship superstructures, vehicle frames, chassis, and vehicle components that are not normally visible during use, such as engine components, motorcycle fairings and fuel tanks, fuel tank surfaces, and other vehicle surfaces exposed to or potentially exposed to fuel, aerospace solvents, and aerospace hydraulic fluids. Any vehicle component that can benefit from a coating as defined herein, whether exposed or hidden from view during normal use, will undergo coating.

[0211] Household and office appliances, furniture, and tools as defined herein are appliances, furniture, and tools used in a home (including a garden) or office environment. These appliances, furniture, and tools may include fabric washer, dishwasher, dryer, refrigerator, stove, microwave oven, computer equipment and printer, air conditioning units, heat pump units, lawn and garden equipment (including lawn furniture, hot tubs, lawnmowers, garden tools, hedge trimmers, lawnmowers (lawn trimmers), chainsaws, garden scrap racks, garden hand tools (e.g., shovels, pitchforks, rakes, and cutting tools)), cabinets, desks, tables, chairs, cupboards, and other items. Any part of any such item that can benefit from coatings as defined herein may undergo coating; such parts include the panels of appliances or furniture and the handles of tools.

[0212] Power industry products may include, for example, pumps, generators, air compressors, industrial heat pumps and air conditioners, batteries, and cement mixers. Any component that benefits from coatings as defined herein may undergo coating; such components include panels and housings.

[0213] Consumer electronics items can include, for example, computers, computer cases, televisions, telephones, pagers, cameras, calculators, printers, scanners, digital decoders, clocks, audio players, headphones, or tablets.

[0214] Building products can be, for example, doors, windows, door frames, window frames, beams or supports, or panels, wall or roofing items used in building construction, or solar panels.

[0215] Products protected by intumescent coatings are typically metal structures (e.g., steel structures) coated with intumescent coatings. Metal structures are often load-bearing components of buildings. Unprotected steel typically begins to soften at around 425°C and loses approximately half its strength by 650°C. Intumescent coatings are used to delay the heating of steel or other substrates. Intumescent coatings can be improved by incorporating a defined acrylic polyester resin into the matrix of the intumescent material before it is applied to the metal substrate to be protected. Typically, the acrylic polyester resin is present in an amount of at least 1 wt%, significantly at least 2 wt%, for example at least 4 wt%, or at least 5%. Typically, the acrylic polyester resin is present in an amount of up to 50 wt%, significantly up to 30 wt%, for example up to 25 wt%, by weight. These definitions refer to the weight of the acrylic polyester resin / intumescent matrix material to be applied to the substrate.

[0216] Articles coated according to the present invention can be classified into two or more of the categories stated above. For example, computer equipment can be considered as household or office supplies, and also as consumer electronics. Beams or supports—building materials—can be coated with an expanding material.

[0217] The products of this invention do not contain metal coils, or food or beverage packaging containers, aerosol cans or tubes, or components used to manufacture such products.

[0218] In the uses defined above, aqueous or powder compositions are generally used to coat surfaces and their components (except for intumescent coatings used as admixtures). A component may comprise multiple surfaces. A component may comprise a portion of a larger component, assembly, or device. A portion of a component may be coated with an aqueous or powder composition as defined herein, or the entire component may be coated.

[0219] The substrate can be new (i.e. newly constructed or manufactured) or it can be refurbished, for example, in the case of refurbishing or repairing components of a car or aircraft.

[0220] As described above, substrates coated with the aqueous or powder compositions of the present invention can include vehicles. For example, the aqueous or powder compositions of the present invention can be used to: coat F / A-18 jet aircraft or related aircraft, such as the F / A-18E Super Hornet and F / A-18F (manufactured by McDonnell Douglas / Boeing and Northrop); coat Boeing 787 Dreamliner, 737, 747, 717 jet aircraft and related aircraft (manufactured by Boeing Commercial Airplanes); coat V-22 Osprey tiltrotor aircraft (V-22...). Osprey); VH-92, S-92 and related aircraft (manufactured by the U.S. Naval Air Systems Command (NAVAIR) and Sikorsky); coated G650, G600, G550, G500, G450 and related aircraft (manufactured by Gulfstream); and coated A350, A320, A330 and related aircraft (manufactured by Airbus). Aqueous or powder compositions can be used as coatings for any suitable commercial, military, or general aviation aircraft, such as those manufactured by Bombardier Inc. and / or Bombardier Aerospace, like the Canada Regional Jet (CRJ) and related aircraft; those manufactured by Lockheed Martin, like the F-22 Raptor, F-35 Lightning, and related aircraft; those manufactured by Northrop Grumman, like the B-2 Spirit strategic bomber and related aircraft; those manufactured by Pilatus Aircraft Ltd.; those manufactured by Eclipse Aviation Corporation; or those manufactured by Eclipse Aerospace (Kestrel Aircraft).

[0221] The water-based or powder coating compositions used in this invention can be applied as a single layer or as part of a multilayer system to a substrate or a portion thereof. Water-based or powder coating compositions can be applied as a single layer. Water-based or powder coating compositions can be applied to an uncoated substrate. For the avoidance of doubt, the uncoated substrate extends to a clean surface prior to application. Water-based or powder coating compositions can be applied as part of a multilayer system over another coating layer. For example, water-based or powder coating compositions can be applied over a primer. Water-based or powder coating compositions can form an intermediate layer or topcoat. Water-based or powder coating compositions can be applied as the first coating layer in a multilayer system. Suitably, water-based or powder coating compositions can be applied as a base coat or primer. Second, third, fourth, etc., coatings can comprise any suitable paint, such as paints containing: for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins or combinations thereof. Second, third, fourth, etc., coatings can comprise polyester resins. Second, third, fourth, etc., coatings can be liquid coatings or powder coatings.

[0222] Those skilled in the art will understand that water-based or powder coating compositions can be applied before or after the formation of a product. For example, a water-based or powder coating composition can be applied to a substrate that is subsequently molded to form a product, or a water-based or powder coating composition can be applied to a product that has already been formed.

[0223] Water-based or powder coating compositions can be applied to a substrate in one or more applications.

[0224] The water-based or powder coating compositions according to the present invention can be applied to a substrate by any suitable method. Methods for applying the water-based or powder coating compositions according to the present invention are well known to those skilled in the art. Suitable application methods for the water-based coating compositions of the present invention include, but are not limited to, the following: electrophoretic coating; spraying; electrostatic spraying; dipping; roller coating; brush coating; etc.

[0225] The aqueous or powder coating compositions of the present invention can be applied to any suitable dry film thickness. The aqueous or powder coating compositions of the present invention can be applied to dry film thicknesses of 2 to 40 micrometers (µm).

[0226] Further information will now be provided regarding suitable application methods for applying a suitable coating composition to a substrate.

[0227] Aqueous compositions can be electrophoretically deposited on any conductive substrate. Suitable substrates include metallic substrates, metallic alloy substrates, and / or metallized substrates, such as nickel-plated plastics. Alternatively, the substrate may include non-metallic conductive materials (including composite materials, e.g., materials comprising carbon fibers or conductive carbon). According to the invention, metals or metallic alloys may include, for example, cold-rolled steel, hot-rolled steel, zinc-coated steel, zinc compounds, or zinc alloys, such as electro-galvanized steel, hot-dip galvanized steel, galvanized annealed steel, nickel-plated steel, and zinc-alloyed steel. The substrate may include aluminum alloys. Non-limiting examples of aluminum alloys include the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as clad aluminum alloys and cast aluminum alloys, such as the A356 series. The substrate may include magnesium alloys. Non-limiting examples of magnesium alloys, such as the AZ31B, AZ91C, AM60B, or EV31A series, may also be used as substrates. The substrates used in this invention may also include other suitable non-ferrous metals (such as titanium or copper) and alloys of these materials.

[0228] The component to be coated may be cylindrical, such as a pipe, and may include, for example, cast iron or steel pipe. The metallic substrate may also be in the form of, for example, a metal sheet or preform. The substrate may also include a conductive or non-conductive substrate at least partially coated with a conductive coating. The conductive coating may include conductive agents such as graphene, conductive carbon black, conductive polymers, or conductive additives. It will also be understood that the substrate may be pretreated with a pretreatment solution. Non-limiting examples of pretreatment solutions include zinc phosphate pretreatment solutions (e.g., those described in U.S. Patent Nos. 4,793,867 and 5,588,989) and zirconium-containing pretreatment solutions (e.g., those described in U.S. Patent Nos. 7,749,368 and 8,673,091). Other non-limiting examples of pretreatment solutions include those comprising 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 solution is a sol-gel, such as those comprising alkoxy-silanes, alkoxy-zirconates, and / or alkoxy-titanates. Alternatively, the substrate can be an untreated substrate, such as a bare substrate, that has not been pretreated with the pretreatment solution.

[0229] The substrate may optionally undergo other treatments prior to coating. For example, the substrate may be cleaned, washed and deoxidized, anodized, pickled, plasma treated, laser treated, or subjected to ion vapor deposition (IVD). These optional treatments may be used alone or in combination with a pretreatment solution.

[0230] The aqueous compositions used in this invention can be used for electrophoretic coatings, which are part of a multilayer coating composite comprising a substrate having various coatings. The coating may optionally comprise a pretreatment layer, such as a phosphate layer (e.g., a zinc phosphate layer) or a metal oxide layer (e.g., a zirconium oxide layer), an electrophoretic coating produced by the aqueous compositions of this invention, optionally one or more primer layers, and suitable one or more topcoats (e.g., a base coat, a clear coat, a colored single-coat, and a color plus clear coat composite composition). It is understood that suitable additional coatings comprise any of those known in the art and may be independently water-based, solvent-based, in the form of solid particles (i.e., powder coating compositions), or in the form of a powder paste. Additional coating compositions may include film-forming polymers, crosslinking materials, and pigments (if a colored base coat or single-coat). One or more primer layers may optionally be disposed between the electrophoretic coating and one or more topcoats. Alternatively, one or more topcoats may be omitted, such that the composite comprises the electrophoretic coating and one or more primer layers.

[0231] Furthermore, one or more topcoats can be applied directly to the electrodepositable coating. In other words, the substrate may be without a primer layer, such that the composite material includes the electrophoretic coating and one or more topcoats. For example, a base coating can be applied directly to at least a portion of the electrodepositable coating.

[0232] It will also be understood that any topcoat layer can be applied over the substrate, even if the substrate is not fully cured. For example, a clear coat can be applied over the base coat even if the base coat has not undergone a curing step (wet-on-wet). The two layers can then be cured during a subsequent curing step, thus eliminating the need to separately cure the base coat and clear coat.

[0233] As used herein, “powder” and similar terms refer to materials that are in the form of solid particles, as opposed to materials in liquid form.

[0234] The powder coating composition of the present invention can be applied by any suitable method. Methods for applying the powder coating composition are well known to those skilled in the art. Suitable application methods include, for example, electrostatic spraying, or application by, for example, supercorona discharge. Suitably, the powder coating composition according to the present invention can be applied by supercorona discharge.

[0235] When the substrate is conductive, powder coating compositions are typically applied electrostatically. Electrostatic spraying usually involves extracting the coating composition from a fluidized bed and propelling it through a corona field. The coating composition particles become charged as they pass through the corona field and are attracted to and deposited on a grounded, conductive substrate—this is grounding. As the charged particles begin to accumulate, the substrate becomes insulating, thus limiting further particle deposition.

[0236] The powder coating composition according to the invention can be applied to any suitable dry film thickness. The powder coating composition according to the invention can be applied to dry film thicknesses of 0.1 µm (micrometer) to 1000 µm, suitably 3 µm to 500 µm, such as 5 µm to 250 µm or even 5 µm to 150 µm, such as 10 µm to 100 µm.

[0237] The average particle size of the powder component of the present invention can be less than 15 micrometers (µm). The average particle size of the powder component can be less than 12 µm, suitably less than 10 µm, such as less than 7.5 µm or even less than 5 µm. For the avoidance of doubt, the term "less than" includes particles having the stated average particle size. For example, "less than 15 µm" refers to particles with an average particle size of 15 µm as well as those with an average particle size lower than this value.

[0238] Particles of these sizes can be produced by any suitable method. Suitable methods are well known to those skilled in the art. Examples of suitable methods include, but are not limited to, cold grinding, milling, and sieving.

[0239] The coating compositions of the present invention may include a liquid carrier in which powder components (such as acid-functionalized polyester materials) are dispersed. For the avoidance of doubt, the dispersion is a powder suspended in a liquid. The coating composition may include any suitable liquid carrier. The liquid carrier may include water, an organic solvent, a mixture of water and one or more organic solvents, or a mixture of organic solvents. Suitably, the liquid carrier may include water.

[0240] According to the present invention, additional components (such as colorants and fillers) can be present in various coating compositions that produce the topcoat. Any suitable colorant and filler can be used. For example, colorants can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings of the present invention. It should be noted that, generally, colorants can be present in any amount sufficient to impart the desired properties, visual and / or color effects in one layer of a multilayer composite material.

[0241] Example colorants include pigments, dyes, and colorants, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effects compositions. Colorants may comprise, for example, finely divided solid powders that are insoluble but wettable under the conditions of use. Colorants may be organic or inorganic, and may be agglomerated or non-agglomerated. Colorants can be incorporated into coatings by grinding or simple mixing. Colorants can be incorporated into coatings by grinding them using a grinding vehicle (such as an acrylic grinding vehicle), the use of which is well known to those skilled in the art.

[0242] Example pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, diazo, naphthol AS, salts (salt lakes), benzimidazolone, condensation, metal complexes, isoindolineone, isoindoline and polycyclic phthalocyanine, quinacridone, dinaphthylbenzene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indigoanthraquinone, anthraquinone pyrimidine, flavinthrone, pinanthraquinone, anthraquinone benzothrone, dioxazine, triaryl cations, quinophthalone pigments, pyrrolopyrrole dione red (“DPP Red BO”), titanium dioxide, carbon black, zinc oxide, antimony oxide, etc., as well as organic or inorganic UV opaque pigments (such as iron oxide), transparent red or yellow iron oxide, phthalocyanine blue and mixtures thereof. The terms “pigment” and “colored filler” are used interchangeably.

[0243] Example dyes include, but are not limited to, solvent-based and / or water-based dyes, such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, dinaphthalene, aluminum, quinacridone, thiazole, thiazide, azo, indigo, nitro, nitroso, oxazine, phthalocyanine, quinoline, symmetrical diphenylethylene, and triphenylmethane.

[0244] Example colorants include, but are not limited to, pigments dispersed in a water-based or water-miscible carrier, such as AQUA-CHEM 896, which is commercially available from Degussa, Inc., CHARISMA COLORANTS, and MAXITONER INDUSTRIAL COLORANTS, which are commercially available from the Accurate Dispersions division of Eastman Chemical, Inc.

[0245] Colorants can be in dispersion form, including, but not limited to, nanoparticle dispersions. Nanoparticle dispersions can contain highly dispersed nanoparticle colorants and / or colorant particles that produce the desired visible color and / or opacity and / or visual effect. Nanoparticle dispersions can contain colorants such as pigments or dyes with particle sizes less than 150 nm, such as less than 70 nm or less than 30 nm. Nanoparticles can be produced from organic or inorganic pigments from milling feedstocks having abrasive media with particle sizes less than 0.5 mm. Example nanoparticle dispersions and methods of their manufacture are identified in U.S. Patent No. 6,875,800 B2, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, vapor-phase condensation, and chemical abrasion (i.e., partial dissolution). To minimize reagglomeration of nanoparticles within a coating, resin-coated nanoparticle dispersions can be used. As used herein, a "resin-coated nanoparticle dispersion" refers to a continuous phase comprising nanoparticles and a resin coating dispersed on the nanoparticles. Example resin-coated nanoparticle dispersions and methods for their manufacture are determined in U.S. Application No. 10 / 876,031, filed June 24, 2004 (which is incorporated herein by reference) and U.S. Provisional Application No. 60 / 482,167, filed June 24, 2003 (which is incorporated herein by reference).

[0246] According to the present invention, special effect compositions that can be used in one or more layers of a multilayer coating composite material comprise pigments and / or compositions that produce appearance effects such as reflection, pearlescent, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, mechanochromism (strain-sensitive pigmentation), iridescence, and / or color change. Additional special effect compositions may provide other perceptible properties such as reflectivity, opacity, or texture. For example, a special effect composition may produce color transfer, such that the color of the coating changes when viewed from different angles. Example color effect compositions are identified in U.S. Patent No. 6,894,086, which is incorporated herein by reference. Additional color effect compositions may comprise transparently coated mica and / or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and / or any composition, wherein interference arises from a difference in refractive index within the material rather than from a difference in refractive index between the material surface and air.

[0247] According to the present invention, photosensitive compositions and / or photochromic compositions can be used in several layers of a multilayer composite material, wherein the color of the photosensitive compositions and / or photochromic compositions reversibly changes upon exposure to a light source. The photochromic and / or photosensitive compositions can be activated by exposure to radiation of a specific wavelength. When the composition is excited, its molecular structure changes, and the altered structure exhibits a new color different from the original color of the composition. When the radiation exposure is removed, the photochromic and / or photosensitive compositions can revert to a resting state, wherein the original color of the composition is restored. For example, the photochromic and / or photosensitive compositions may be colorless in the unexcited state and exhibit color in the excited state. The complete color change can occur within milliseconds to minutes (e.g., 20 to 60 seconds). Example photochromic and / or photosensitive compositions contain photochromic dyes.

[0248] Photosensitive compositions and / or photochromic compositions may be associated with and / or at least partially bound to polymeric materials of polymers and / or polymerizable components, such as by covalent bonding. Unlike some coatings in which photosensitive compositions can migrate out of the coating and crystallize into the substrate, the migration outside the coating of photosensitive compositions and / or photochromic compositions associated with and / or at least partially bound to polymeric components according to the invention is minimal. Example photosensitive compositions and / or photochromic compositions and methods of their manufacture are identified in U.S. Application Serial No. 10 / 892,919, filed July 16, 2004, and are incorporated herein by reference.

[0249] The primer and / or one or more topcoats may optionally further include corrosion inhibitors. The corrosion inhibitors may include any of the corrosion inhibitors discussed above with respect to water-based or powder compositions, and may further include magnesium oxide, magnesium hydroxide, lithium salts, and / or lithium silicates.

[0250] According to the present invention, aqueous or powder compositions and / or layers deposited from said aqueous or powder compositions, as well as any pretreatment layers, primer layers, or topcoats, may be substantially free of, essentially free of, or completely free of chromium or chromium-containing compounds. As used herein, the term "chromium-containing compound" refers to a material containing trivalent or hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic anhydride, dichromates such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium dichromate, barium dichromate, magnesium dichromate, zinc dichromate, cadmium dichromate, and strontium dichromate. When aqueous or powder compositions and / or layers deposited from said aqueous or powder compositions, as well as any pretreatment layers, primer layers, or topcoats, are substantially free of, essentially free of, or completely free of chromium, this includes chromium in any form, such as, but not limited to, the trivalent and hexavalent chromium-containing compounds listed above.

[0251] The statement that an aqueous or powder composition and / or a layer deposited from said aqueous or powder composition, as well as any pretreatment layer, primer layer, or topcoat layer, is substantially free of chromium or chromium-containing compounds means that chromium or chromium-containing compounds are not intentionally added, but may be present in trace amounts due to impurities or unavoidable environmental contamination. 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 chromium or chromium-containing compounds are not present in the aqueous or powder composition and / or a layer deposited from said aqueous or powder composition, as well as any pretreatment layer, primer layer, or topcoat layer, at a level that would be environmentally burdensome. The term "substantially free" means that the aqueous or powder composition and / or a layer deposited from said aqueous or powder composition, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 10 ppm of chromium (based on the total solid weight of the composition, layer, or multilayer, if any). The term "fundamentally free of" means that the aqueous or powder composition and / or the layer deposited from said aqueous or powder composition, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 1 ppm of chromium (based on the total solid weight of the composition, layer, or multilayer, if any). The term "completely free of" means that the aqueous or powder composition and / or the layer comprising said aqueous or powder composition, as well as any pretreatment layer, primer layer, or topcoat layer, contains less than 1 ppb of chromium (based on the total solid weight of the composition, layer, or multilayer, if any).

[0252] According to the present invention, the coating deposited from the aqueous or powder composition described above can be hydrolytically stable, as determined by a hydrolytic stability test method. As used herein, a "hydrolytic stability test method" refers to immersing a baked panel in deionized water at 90°C for 24 hours. The panel is then removed and set to 150°C. Bake in an oven for 60 minutes to dehydrate the coating film. Then, retest the curing of the panel according to the Double Acetone Rub Test Method. Whether a coating is considered hydrolytically stable is demonstrated by its ability to retain acetone resistance after water immersion, compared to the acetone resistance of an un-water-immersed coating. Specifically, the number of double acetone rubs the coating survives after water immersion is compared to the number of double acetone rubs the coating survives without water immersion. If the number of double acetone rubs the coating survives after water immersion without touching the underlying substrate is at least 60% of the number of double acetone rubs the coating would survive without water immersion, the coating is considered "hydrolytically stable." Note: If the cured coating survives 100 or more double acetone rubs without water immersion (if the coating survives at least 60 double acetone rubs without touching the substrate), the cured coating is considered hydrolytically stable. For example, if a paint survives at least 30 diacetone rubs after exposure to water, a paint that survives 50 diacetone rubs without exposure to water is considered hydrolytically stable. Although this refers to paints before and after exposure to water, it should be understood that two different coated panels were used, each coated with the same composition using the same technique and cured under the same conditions (i.e., the same oven, oven temperature, and baking time).

[0253] As used herein, unless otherwise expressly stated, all figures, such as those indicating values, ranges, quantities, or percentages, may be interpreted as beginning with the word "about," even if the term is not explicitly stated. Furthermore, all numerical ranges described herein are intended to encompass all subranges described herein. The singular encompasses the plural, and vice versa. For example, although this document refers to "a" first polyester material, "a" powder coating aqueous or powder coating composition, "an" base coating aqueous or powder coating composition, "an" isocyanate resin, "an" the residue of "the," etc., one or more of each of these may be used, along with any other components. As used herein, the term "polymer" refers to both oligomers and homopolymers and copolymers, and the prefix "poly" indicates two or more. The inclusion of similar terms means, for example, including, but not limited to. Furthermore, although the present invention has been described in terms of "comprising", the processes, materials, and water-based or powder coating compositions described in detail herein may also be described as "fundamentally composed of" or "consisting of".

[0254] All the features contained in this article can be combined in any combination.

[0255] To better understand the present invention and to illustrate how embodiments of the invention can be implemented, reference will now be made to the following theoretical and experimental data by way of example.

[0256] Example

[0257] Acrylic modified polyester resin - Examples 1-8

[0258] Table 1 shows detailed information on polyester precursor examples 1 to 8. Each example from 1 to 8 illustrates the composition of the polyester material. Examples 1 to 4 show unsaturated hydroxyl-functionalized polyesters having TMCD and 5-SSIPA. Examples 5 to 8 show unsaturated hydroxyl-functionalized polyesters having TMCD but not 5-SSIPA.

[0259] The polyester materials in Examples 1 to 8 are formed as follows. 2-Methyl-1,3-propanediol, polyol (TMCD), cyclohexanediethanol, 5-SSIPA, dibutyltin oxide, dimethyl terephthalate, hexahydrophthalic anhydride, and cyclohexane-1,4-dicarboxylic acid are added as a batch to a vessel equipped with a steam column, distillation head, and condenser. The batch temperature is raised to 150°C by stirring at 400 rpm under a N2 cover. Once the temperature reaches 150°C, the batch temperature is raised to 230°C over a 4-hour period (in 10°C increments every 30 minutes), while ensuring the head temperature remains below 100°C.

[0260] Once the batch reaches 230°C, assess the acid value hourly. When the acid value is less than 15, cool the batch to 150°C and add methyl hydroquinone. After 10 minutes, add maleic anhydride and raise the batch temperature to 195°C until the acid value increases to approximately 20. Then cool the batch to 130°C and perform azeotropic separation using a Dean Starktrap separator.

[0261] The polyester materials of Examples 1 to 8 underwent a grafting process to graft acrylic acid onto the unsaturated functionalities of the polyester backbone (as endowed by maleic anhydride) to form acrylic acid-modified polyester resins 1 to 8 (simply referred to as resins 1 to 8 in Table 2). Details of the monomers used in the acrylic acid grafting reaction are shown in Table 2.

[0262] The acrylic-modified polyester resin was formed as follows: The polyester material (Examples 1 to 8) was added to a vessel, mixed at 225 rpm, and heated to 120°C. Once at 120°C, the acrylate monomer was added over a period of 75 minutes with continuous stirring. Then, Dowanol DPM and t-butyl peroctoate initiator were added over a period of 90 minutes, and the reaction was maintained at 120°C for an additional 45 minutes. The reaction mixture was then cooled to below 80°C.

[0263] The acrylic-modified polyester resin is used to form an aqueous dispersion having the components shown in Table 3.

[0264] An acrylic-modified polyester resin is heated to 80°C to 85°C, and then deionized water is slowly added to the resin (over a period of approximately 60 minutes) while maintaining the elevated temperature (80°C to 85°C). The dispersed mixture is then stirred and kept at 80°C to 85°C for an additional 60 minutes to form an aqueous dispersion. The aqueous dispersion is then cooled.

[0265] In forming an aqueous dispersion in which the polyester material does not contain sulfonated monomers, dimethylethanolamine is added to heated (80°C to 85°C) acrylic-modified polyester resin and stirred for 10 minutes until homogeneous, then deionized water is added. Otherwise, the process is the same.

[0266] An aqueous dispersion is formed into an aqueous coating composition having the components shown in Table 4, as follows. A crosslinking material (Cymel 1123-phenylmelamine, available from Allnex), a capped DDBSA catalyst (Nacure 5925, available from King), and a wax additive (Michem Lube 160, available from Michelman) are stirred into an aqueous PGA dispersion to form an aqueous coating composition suitable for use as a coating composition on vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by intumescent coatings as described in this specification.

[0267] Table 1

[0268]

[0269] Table 2

[0270]

[0271] Table 3

[0272]

[0273] Table 4

[0274]

[0275] Certain aspects of the present invention can be combined in the following combinations.

[0276] 1. A product having at least a portion thereof coated with a coating, said product being a vehicle product, household or office appliance, furniture or tool, power industry product, consumer electronics, building product, or product protected by an intumescent coating, said coating being derived from a water-based coating composition or a powder coating composition, said coating composition comprising:

[0277] (a) An acrylic polyester resin, which can be obtained by grafting an acrylic polymer with a polyester material, said polyester material being obtained by polymerizing the following:

[0278] i) Polybasic acid components, and

[0279] ii) A polyol component comprising a compound including 2,2,4,4-tetraalkylcyclobutane-1,3-diol.

[0280] The polyacid component or one of the polyol components includes a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0281] (b) Crosslinked materials.

[0282] 2. A method of coating at least a portion of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating, said method comprising applying a coating composition to at least a portion of the surface of said product, said coating composition comprising an aqueous coating composition or a powder coating composition, said coating composition comprising an acrylic-modified polyester resin and a crosslinking material, said acrylic-modified polyester resin being obtainable by grafting an acrylic polymer onto a polyester material, said polyester material being obtainable by polymerizing the following:

[0283] i) Polybasic acid components, and

[0284] ii) A polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol

[0285] The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0286] And to cure the aqueous or powder composition to form a coating.

[0287] 3. Use of a coating composition derived from an aqueous composition or powder composition comprising an acrylic-modified polyester resin and a crosslinking material, wherein the acrylic-modified polyester resin can be obtained by grafting an acrylic polymer onto a polyester material, the polyester material being obtained by polymerizing the following:

[0288] i) Polybasic acid components, and

[0289] ii) A polyol component comprising a compound including 2,2,4,4-tetraalkylcyclobutane-1,3-diol.

[0290] The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality.

[0291] The coating composition is used to coat at least a portion of the surface of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating.

[0292] 4. The product, method, or use according to any of the foregoing aspects, wherein the functional monomer comprises an olefinically unsaturated monomer.

[0293] 5. The product, method, or use according to any of the foregoing aspects, wherein the functional monomer comprises: maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, medaconic acid, medaconic anhydride, phenylmaleic acid, phenylmaleic anhydride, tert-butylmaleic acid, tert-butylmaleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methylmaleic acid; and / or methylmaleic anhydride.

[0294] 6. The product, method, or use according to any of the foregoing aspects, wherein the polybasic acid component comprises: dimethyl terephthalate, isophthalic acid, hexahydrophthalic anhydride; and / or cyclohexane-1,4-dicarboxylic acid.

[0295] 7. The product, method, or use according to any of the foregoing aspects, wherein the 2,2,4,4-tetraalkylcyclobutane-1,3-diol comprises 2,2,4,4-tetramethylcyclobutane-1,3-diol (“TMCD”).

[0296] 8. The product, method, or use according to any of the foregoing aspects, wherein the polyol component comprises 2,2,4,4-tetraalkylcyclobutane-1,3-diol in combination with 2-methyl-1,3-propanediol and / or cyclohexanediol.

[0297] 9. The product, method, or use according to any of the foregoing aspects, wherein the polyacid component and / or the polyol component comprises a sulfonated monomer.

[0298] 10. The product, method, or use according to any of the foregoing aspects, wherein the sulfonated monomer comprises: 5-(sodium sulfonate)-isophthalic acid; dimethyl 5-(sodium sulfonate)isophthalate; 5-(lithium sulfonate)isophthalic acid; and / or bis(2-hydroxyethyl) 5-(sodium sulfonate)isophthalate.

[0299] 11. The product, method, or use according to any of the foregoing aspects, wherein the polyester material comprises Mn from 1,000 Daltons (Da = g / mol) to 15,000 Da.

[0300] 12. The product, method, or use according to any of the foregoing aspects, wherein the acrylic polyester resin is formed from the polyester material and the acrylic modified polymer in a weight ratio of 85 wt% to 55 wt% polyester material to 45 wt% to 15 wt% acrylic modified polymer.

[0301] 13. The product, method, or use according to any of the foregoing aspects, wherein the acrylic-modified polymer is polymerized in the presence of the polyester material to form an acrylic-modified polyester resin.

[0302] 14. The product, method, or use according to any of the foregoing aspects, wherein the acrylic modified polymer is formed from: methyl methacrylate; ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid; cyclohexyl methacrylate, allyl methacrylate, dimethylaminoethyl methacrylate, butylaminoethyl methacrylate, and / or HEMA phosphate (such as ethylene glycol methacrylate).

[0303] 15. The product, method, or use according to any of the foregoing aspects, wherein the crosslinking material comprises phenolic resin, benzo-melamine, and / or melamine.

[0304] 16. The product, method, or use according to any of the foregoing aspects, wherein the coating composition is substantially free of bisphenol A (BPA), bisphenol F (BPF), and derivatives thereof.

[0305] 17. The product, method, or use according to any of the foregoing aspects, wherein the coating composition is substantially free of styrene.

[0306] 18. The product, method, or use according to any of the foregoing aspects, wherein the coating composition is substantially free of formaldehyde.

[0307] 19. The product, method, or use according to any of the foregoing aspects, wherein the coating composition further comprises an adhesion promoter.

[0308] 20. The product, method, or use according to any of the foregoing aspects, wherein the adhesion promoter comprises an acidic polyester material.

[0309] 21. The product, method, or use according to aspect 20, wherein the acidic polyester typically comprises the reaction product of the following substances:

[0310] (a) A polyester having an Mn of 2000 to 10,000, a hydroxyl number of 20 to 75, and an acid value of 15 to 25; said polyester being a condensation polymer of the following substances:

[0311] (i) Polyol components comprising a mixture of diols and triols,

[0312] (ii) Polyacid components including α,β-olefinically unsaturated polycarboxylic acids,

[0313] as well as

[0314] (b) Phosphorous acid.

[0315] 22. The product, method, or use according to any of the foregoing aspects, wherein the Tg of the polyester material is 25°C or higher.

[0316] 23. The product, method, or use according to any of the foregoing aspects, wherein the Tg of the acrylic polyester resin is 25°C or higher.

[0317] 24. The product, method, or use according to any of the foregoing aspects, wherein the coating formed from the coating composition has a Tg of 25°C or higher.

[0318] 25. The product, method, or use according to any of the foregoing aspects, wherein the product is a vehicle product as part of an aircraft, spacecraft, watercraft, or land vehicle, said part being selected from doors, body panels, trunk lids, roof panels, hoods, roofs, longitudinal struts, rivets, wheels, landing gear assemblies, shells used on aircraft, hulls, ship superstructures, vehicle frames, chassis, engine components, motorcycle fairings and fuel tanks, fuel tank surfaces, and other vehicle surfaces exposed to or potentially exposed to fuel, aerospace solvents, and aerospace hydraulic fluids.

[0319] 26. The product, method, or use according to any of the foregoing aspects, wherein the means of transport is an airplane, a car, a truck, a bus, a tractor, or a ship.

[0320] 27. The product, method, or use according to any of the foregoing aspects, wherein the household or office appliance, furniture, or tool is a fabric washer, dishwasher, dryer, refrigerator, cabinet, or desk.

[0321] 28. The product, method, or use according to any of the foregoing aspects, wherein the power industrial product is a pump, air compressor, heat pump, or air conditioner.

[0322] 29. The product, method, or use according to any of the foregoing aspects, wherein the consumer electronic article is a computer, television, telephone, or camera.

[0323] 30. The product, method, or use according to any of the foregoing aspects, wherein the building product is a door, window, door frame, window frame, beam or bracket, or a panel, wall article or roof article for building construction, or a solar panel.

[0324] 31. The product, method, or use according to any of the foregoing aspects, wherein the product is protected by an intumescent coating and is a metal structure thereon coated with the intumescent coating, wherein the intumescent coating composition incorporates the acrylic polyester resin into the matrix of the intumescent material before it is coated onto the metal structure to be protected.

Claims

1. A product having at least a portion thereof coated with a coating, said product being a vehicle product, household or office appliance, furniture or tool, power industry product, consumer electronics, building product, or product protected by an intumescent coating, said coating being derived from a water-based coating composition or a powder coating composition, said coating composition comprising: (a) An acrylic polyester resin, which can be obtained by grafting an acrylic polymer onto a polyester material, said polyester material being obtained by polymerizing the following: i) Polybasic acid components, and ii) A polyol component comprising a compound including 2,2,4,4-tetraalkylcyclobutane-1,3-diol. The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that the acrylic polymer can be grafted onto the polyester material using the functionality. (b) Crosslinked materials.

2. A method of coating at least a portion of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating, said method comprising applying a coating composition to at least a portion of the surface of said product, said coating composition comprising an aqueous coating composition or a powder coating composition, said coating composition comprising an acrylic-modified polyester resin and a crosslinking material, said acrylic-modified polyester resin being obtainable by grafting an acrylic polymer onto a polyester material, said polyester material being obtainable by polymerizing the following: i) Polybasic acid components, and ii) A polyol component comprising 2,2,4,4-tetraalkylcyclobutane-1,3-diol The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that an acrylic polymer can be grafted onto the polyester material using the functionality. And to cure the aqueous or powder composition to form a coating.

3. Use of a coating composition derived from an aqueous composition or powder composition comprising an acrylic-modified polyester resin and a crosslinking material, wherein the acrylic-modified polyester resin can be obtained by grafting an acrylic polymer onto a polyester material, the polyester material being obtained by polymerizing the following: i) Polybasic acid components, and ii) A polyol component comprising a compound including 2,2,4,4-tetraalkylcyclobutane-1,3-diol. The polyacid component or one of the polyol components comprises a functional monomer that can be manipulated to impart functionality to the polyester resin, such that an acrylic polymer can be grafted onto the polyester material using the functionality. The coating composition is used to coat at least a portion of the surface of products selected from: vehicle products, household or office appliances, furniture or tools, power industry products, consumer electronics, building products, or products protected by an intumescent coating.

4. The product, method, or use according to claim 1, 2, or 3, wherein the functional monomer comprises an olefinically unsaturated monomer.

5. The product, method, or use according to claim 1, 2, or 3, wherein the functional monomer comprises: Maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, medaconic acid, medaconic anhydride, phenylmaleic acid, phenylmaleic anhydride, tert-butylmaleic acid, tert-butylmaleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methylmaleic acid; and / or methylmaleic anhydride.

6. The product, method, or use according to claim 1, 2, or 3, wherein the polybasic acid component comprises: Dimethyl terephthalate, isophthalic acid, hexahydrophthalic anhydride; And / or cyclohexane-1,4-dicarboxylic acid.

7. The product, method, or use according to claim 1, 2, or 3, wherein the 2,2,4,4-tetraalkylcyclobutane-1,3-diol comprises 2,2,4,4-tetramethylcyclobutane-1,3-diol ("TMCD").

8. The product, method, or use according to claim 1, 2, or 3, wherein the polyol component comprises 2,2,4,4-tetraalkylcyclobutane-1,3-diol in combination with 2-methyl-1,3-propanediol and / or cyclohexanediol.

9. The product, method, or use according to claim 1, 2, or 3, wherein the polyacid component and / or the polyol component comprises a sulfonated monomer.

10. The product, method, or use according to claim 1, 2, or 3, wherein the sulfonated monomer comprises: 5-(sodium sulfonate)-isophthalic acid, dimethyl 5-(sodium sulfonate)isophthalate, 5-(lithium sulfonate)isophthalic acid; and / or bis(2-hydroxyethyl) 5-(sodium sulfonate)isophthalate.

11. The product, method, or use according to claim 1, 2, or 3, wherein the polyester material comprises Mn from 1,000 Daltons (Da = g / mol) to 15,000 Da.

12. The product, method, or use according to claim 1, 2, or 3, wherein the acrylic polyester resin is formed from the polyester material and the acrylic modified polymer in a weight ratio of 85 wt% to 55 wt% polyester material to 45 wt% to 15 wt% acrylic modified polymer.

13. The product, method, or use according to claim 1, 2, or 3, wherein the acrylic-modified polymer is polymerized in the presence of the polyester material to form an acrylic-modified polyester resin.

14. The product, method, or use according to claim 1, 2, or 3, wherein the acrylic modified polymer is formed from: methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid; cyclohexyl methacrylate, allyl methacrylate, dimethylaminoethyl methacrylate, butylaminoethyl methacrylate; and / or HEMA phosphate (such as ethylene glycol methacrylate).

15. The product, method, or use according to claim 1, 2, or 3, wherein the crosslinking material may include phenolic resin; benzoic melamine; and / or melamine.

16. The product, method, or use according to claim 1, 2, or 3, wherein the coating composition is substantially free of bisphenol A (BPA), bisphenol F (BPF), and derivatives thereof.

17. The product, method, or use according to claim 1, 2, or 3, wherein the coating composition is substantially free of styrene.

18. The product, method, or use according to claim 1, 2, or 3, wherein the coating composition is substantially free of formaldehyde.

19. The product, method, or use according to claim 1, 2, or 3, wherein the coating composition further comprises an adhesion promoter.

20. The product, method, or use according to claim 1, 2, or 3, wherein the adhesion promoter comprises an acidic polyester material.

21. The product, method, or use according to claim 20, wherein the acidic polyester typically comprises the reaction product of the following substances: (a) A polyester having an Mn of 2000 to 10,000, a hydroxyl number of 20 to 75, and an acid value of 15 to 25; said polyester being a condensation polymer of the following substances: (i) Polyol components comprising a mixture of diols and triols, (ii) Polyacid components including α,β-olefinically unsaturated polycarboxylic acids, as well as (b) Phosphorous acid.

22. The product, method, or use according to claim 1, 2, or 3, wherein the Tg of the polyester material is 25°C or higher.

23. The product, method, or use according to claim 1, 2, or 3, wherein the Tg of the acrylic polyester resin is 25°C or higher.

24. The product, method, or use according to claim 1, 2, or 3, wherein the coating formed from the coating composition has a Tg of 25°C or higher.

25. The product, method, or use according to claim 1, 2, or 3, wherein the product is a vehicle product as part of an aircraft, spacecraft, watercraft, or land vehicle, said part being selected from doors, body panels, trunk lids, roof panels, hoods, roofs, longitudinal struts, rivets, wheels, landing gear assemblies, shells used on aircraft, hulls, ship superstructures, vehicle frames, chassis, engine components, motorcycle fairings and fuel tanks, fuel tank surfaces, and other vehicle surfaces exposed to or potentially exposed to fuel, aerospace solvents, and aerospace hydraulic fluids.

26. The product, method, or use according to claim 1, 2, or 3, wherein the means of transport is an airplane, car, truck, bus, tractor, or ship.

27. The product, method, or use according to claim 1, 2, or 3, wherein the household or office appliance, furniture, or tool is a fabric washer, dishwasher, dryer, refrigerator, cabinet, or desk.

28. The product, method, or use according to claim 1, 2, or 3, wherein the power industrial product is a pump, air compressor, heat pump, or air conditioner.

29. The product, method, or use according to claim 1, 2, or 3, wherein the consumer electronic article is a computer, television, telephone, or camera.

30. The product, method, or use according to claim 1, 2, or 3, wherein the building product is a door, window, door frame, window frame, beam or bracket, or a panel, wall article, or roof article for building construction, or a solar panel.

31. The product, method, or use according to claim 1, 2, or 3, wherein the product is protected by an intumescent coating and is a metal structure thereon coated with the intumescent coating, wherein the intumescent coating composition incorporates the acrylic polyester resin into the matrix of the intumescent material before it is coated onto the metal structure to be protected.

Images