Coating compositions and articles coated therewith

Abstract

This invention discloses a topcoat composition comprising a film-forming resin, a crosslinking material, a lubricant, and at least one additive. The topcoat composition may further comprise an organosilicon copolymer and precipitated silica. The topcoat composition may be substantially free of perfluorinated and polyfluorinated substances (PFAS) and their derivatives, such as polytetrafluoroethylene (PTFE).

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 602,124, filed November 22, 2023, entitled “Coating Compositions and Articles Coated Therewith,” pursuant to 35 USC § 119(e), which is incorporated herein by reference in its entirety.

[0003] Government licensing rights

[0004] This invention was completed with government funding, under contract number W911NF-17-2-0227, awarded by the U.S. Army Contract Command on behalf of the U.S. Army Research Laboratory (ARL). The government may own certain rights to this invention. Technical Field

[0005] This disclosure relates to topcoat coating compositions that can be used to coat a variety of substrates, including packaging articles such as food and / or beverage cans. Background Technology

[0006] Various coatings have been used to coat the surfaces of packaging articles, such as food and beverage cans. For example, sometimes a "roll coating" or "sheet coating" operation is used to coat metal cans; that is, a flat roll or sheet of a suitable substrate (e.g., steel or aluminum) is coated with a suitable composition and then cured (e.g., cured). The coated substrate is then formed into can ends or can bodies. Alternatively, the coating composition can be applied (e.g., by spraying, dipping, rolling, etc.) to a formed article and then cured.

[0007] Packaging coatings can be applied to substrates at high speeds and, upon curing, provide the necessary properties to meet the demands of such end-use applications. For example, the outer coating of packaging articles should provide lubricity and abrasion resistance, excellent adhesion to the substrate, durability, and resistance to degradation over extended periods, even when exposed to harsh environments.

[0008] In the manufacture of two-piece metal cans for containing beverages, etc., the can body is formed, and before the can body is filled and the top is placed in place, the can is decorated, such as by first applying a primer and printing a label on the can, and then applying a topcoat layer. External protective can coatings, such as topcoats, typically contain lubricants (e.g., waxes), which benefit the manufacture and transport of metalworking products (e.g., food or beverage cans, can ends, metal caps for food containers, etc.) by imparting lubricity and / or abrasion resistance to the coated metal substrate sheet. However, these lubricants often contain polytetrafluoroethylene (PTFE) wax. Perfluorinated and polyfluorinated substances (PFAS) are commonly used in the formulation of PTFE-based waxes. Some people wish to reduce or eliminate PFAS in coating compositions.

[0009] Furthermore, beverage manufacturers are increasingly inclined to use tactile inks on beverage cans, which provide a non-smooth surface to give users a tactile feel when gripping the can and / or drinking the beverage. A topcoat coating is required to accommodate both smooth and tactile surfaces, which presents additional challenges.

[0010] Therefore, there is a need for improved lubricant systems used in coatings, such as packaging coatings. Summary of the Invention

[0011] This disclosure provides a topcoat composition comprising: a film-forming resin; a crosslinking material; a lubricant; and at least one additive. The lubricant is at least one selected from polyethylene wax, Fischer-Tropsch wax, and bio-wax. The topcoat composition is substantially free of perfluorinated and polyfluorinated substances.

[0012] This disclosure further provides a package having at least a portion of its outer surface coated with a topcoat derived from a coating composition comprising: a film-forming resin; a crosslinking material; a lubricant; and at least one additive.

[0013] This disclosure provides a method for coating food and / or beverage packaging, comprising: coating at least a portion of the outer surface of the food and / or beverage packaging with a topcoat composition comprising a film-forming resin, a crosslinking material, a lubricant, and at least one additive. The lubricant comprises at least one selected from polyethylene wax, Fischer-Tropsch wax, and bio-wax. Furthermore, the coating composition is substantially free of perfluorinated and polyfluorinated substances (PFAS).

[0014] This disclosure additionally provides a method for coating food and / or beverage packaging, comprising: coating at least a portion of the outer surface of the food and / or beverage packaging with a topcoat composition comprising a film-forming resin, a crosslinking material, a lubricant, a silicone-modified polymer, precipitated silica, and at least one additive. The lubricant comprises Fischer-Tropsch wax. Furthermore, the coating composition is substantially free of perfluorinated and polyfluorinated compounds (PFAS). Attached Figure Description

[0015] The above and other features and advantages of this disclosure, as well as the ways in which they are obtained, will become more apparent from the following description taken in conjunction with the accompanying drawings, and the disclosure itself will be better understood. The above and other features of this disclosure can be used in any combination or arrangement.

[0016] Figure 1 This is a graph showing the failure cycles and coefficient of friction for each of the present invention compositions 2-10 and comparative compositions 2-7. Detailed Implementation

[0017] This disclosure provides a topcoat coating composition for coating glossy and tactile substrates, such as food and / or beverage cans.

[0018] I. Definition

[0019] For the purposes of the following detailed description, it should be understood that this disclosure may take various alternative variations and sequences of steps unless the contrary is explicitly stated. Furthermore, except in any operational instance, or where otherwise indicated, all figures used in the specification and claims to indicate, for example, the quantity of an ingredient, should be understood to be modified by the term “about” in all cases. For example, numerical ranges provided for the weight percentage of a component or the amount of added component should be interpreted as being modified by the term “about.” Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties to be obtained through this disclosure. At least, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0020] Although the numerical ranges and parameters described in this disclosure are approximate, the values ​​illustrated in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding test measurement results.

[0021] Although specific examples of this disclosure have been described above for illustrative purposes, it will be apparent to those skilled in the art that many changes may be made to the details of this disclosure without departing from the scope of the disclosure as defined in the appended claims.

[0022] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges thereof. For example, the range “1 to 10” is intended to include all subranges from the stated minimum value of 1 to the stated maximum value of 10 (and include both the minimum and maximum values), that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0023] Unless otherwise specified, the use of the singular includes the plural and the plural encompasses the singular. Furthermore, unless otherwise specified, the use of "or" means "and / or," even if "and / or" may be explicitly used in certain instances.

[0024] As used herein, a "topcoat" refers to a substantially transparent cured coating that allows the substrate and / or underlying coatings (such as printed labels) to be visible through it. Topcoats can provide a glossy or matte finish on the substrate.

[0025] As used in this article, "topcoat composition" refers to a coating composition that can be used to provide a topcoat layer.

[0026] As used herein, "a topcoat layer derived from a topcoat composition" means applying a topcoat composition to a substrate and curing it to provide a topcoat layer on the substrate.

[0027] As used herein, “substantially transparent” describes a topcoat or topcoat composition containing less than 5 wt% pigment, such as less than 3 wt%, such as less than 1 wt%, or even less than 0.5 wt% pigment, based on the total solid weight of the topcoat or topcoat composition.

[0028] The term “pigment” as used in this article refers to any additive that imparts color to a coating (rather than texture, such as matte or satin texture).

[0029] This article uses the term "wax" to describe materials formed from mixtures and / or modified alkanes of various chain lengths, which also include other functional groups in the chain, such as esters and / or amines, and can exhibit phase change properties. Waxes tend to be solid at room temperature (20°C), have a melting point above about 40°C, and are able to absorb heat while exhibiting minimal volume change during melting.

[0030] Fischer-Tropsch (FT) wax is a purely synthetic polymer synthesized from carbon monoxide and hydrogen, and can be considered a mineral wax. FT wax has long chains (C... 12(or more carbon atoms) aliphatic hydrocarbons with relatively short side chains.

[0031] Polyethylene wax is a low molecular weight synthetic polymer containing ethylene monomer chains. The typical melting point of polyethylene wax is in the range of 90°C to 150°C.

[0032] "Biowaxes" are a group of organic polymers formed from bio-based components, such as blueberry wax, candelilla wax, carnauba wax, cotton wax, Spanish grass wax, orriculi wax, palm wax, rice bran wax, soybean wax, and sugarcane wax.

[0033] This article uses the term "PFAS" to describe perfluorinated and polyfluorinated substances, including synthetic organofluorine compounds in which multiple fluorine atoms are attached to an alkyl chain, such as perfluorinated monomers and oligomers, such as perfluorooctanoic acid.

[0034] This article uses the term "wet" coating composition to describe liquid coating compositions prior to curing.

[0035] This article uses the term "dry" coating composition to describe the coating composition after curing.

[0036] II. Topcoat Composition

[0037] This disclosure provides a topcoat composition comprising a film-forming resin, a crosslinking material, and a lubricant, wherein the topcoat composition is substantially free of polytetrafluoroethylene. Furthermore, the topcoat composition may further comprise an organosilicon copolymer, precipitated silica, and additives. This topcoat composition can be applied to the glossy and tactile surfaces of a substrate, such as food / beverage cans or packaging.

[0038] Food and / or beverage packaging with a topcoat layer coated on at least its outer portion is also provided, the topcoat layer being derived from the topcoat coating compositions previously described and further described below.

[0039] Food and / or beverage packaging (i.e., the substrate) may be coated with a clear coat on at least a portion of its outer surface. Food and / or beverage packaging may be coated with other coatings besides the clear coat. The clear coat may be applied over a primer, undercoat, and / or ink layer. The clear coat may form a surface coating, such as over an ink layer.

[0040] The substrate may include a tactile surface or other textured surface with visual images, brand logos, and other illustrations. The clear coat compositions disclosed herein can be used to provide protective properties without impairing the visual and textural properties of the substrate surface. The clear coat compositions may include a lubricant wax, a silicone-modified polymer, and precipitated silica, resulting in a low coefficient of friction suitable for maintaining the textural properties of the coated substrate surface. The high surface area and high oil absorption properties of the precipitated silica attract the silicone-modified polymer, thereby allowing the lubricant wax to migrate to the surface of the clear coat composition. As the wax migrates to the surface of the composition, the coefficient of friction is reduced, and a desiccant effect is achieved. Due to its low coefficient of friction, the clear coat composition can coat the textured surface of the substrate without obscuring the tactile properties of the substrate.

[0041] The topcoat layer can be derived from any topcoat composition described herein. Therefore, the characteristics of the topcoat layer disclosed herein also apply to the topcoat composition, and vice versa.

[0042] A. Film-forming resin

[0043] The topcoat composition comprises a film-forming resin. The topcoat composition may comprise any suitable film-forming resin. The film-forming resin may comprise a functionalized resin such that it contains functional groups capable of reacting with a crosslinking material, thereby allowing the resin to crosslink. Suitable such functional groups include epoxy, ester, amide, ketone, vinyl, hydroxyl, and / or carboxyl groups, or any combination thereof. The film-forming resin may comprise polyester resins, polyol resins, polyurethane resins, epoxy resins, and / or acrylic resins.

[0044] The topcoat composition may contain 40 wt.%, 50 wt.%, 60 wt.% to 70 wt.%, 80 wt.%, 98 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 40 wt.% to 98 wt.%, 50 wt.% to 80 wt.%, or 60 wt.% to 70 wt.%, of film-forming resin, wherein wt.% is based on the total “wet” weight of the topcoat composition.

[0045] The topcoat layer may contain 60 wt.%, 62 wt.%, 64 wt.% to 66 wt.%, 70 wt.%, 75 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 60 wt.% to 75 wt.%, 62 wt.% to 70 wt.%, or 64 wt.% to 66 wt.%, of film-forming resin, where wt.% is based on the total “dry” weight of the topcoat layer.

[0046] i. Acrylic polymers

[0047] Film-forming resins may include acrylic polymers and / or polyester polymers. Acrylic polymers may be polymers derived from one or more acrylic monomers. Additionally, blends of acrylic polymers may be used. Acrylic polymers may comprise graded acrylic polymers and / or polyester-grafted acrylic resins.

[0048] Film-forming resins may include polyacrylate resins. Polyacrylate (co)polymers may be formed from C1 to C6 alkyl (C0 to C1 alkoxy) acrylate monomer units. C1 to C6 alkyl (v-alkoxy) acrylate materials may include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. C1 to C6 alkyl (C0 to C1 alkoxy) acrylates may contain functional groups such as epoxy, hydroxy, or alkoxymethyl ethers. C1 to C6 alkyl (C0 to C1 alkoxy) acrylates may include glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, or n-butoxymethacrylamide. The reaction mixture may further contain olefinically unsaturated monomers. The reaction mixture may contain aryl-substituted olefinically unsaturated monomers, such as styrene.

[0049] Suitable polyacrylate (co)polymers may contain hydroxyl or acid functionalized solution-type acrylic resins, such as Paraaloid AT-746, Paraaloid AT-63, Paraaloid AT-81, Paraaloid AT-147, Paraaloid AT-85, or Paraaloid AT-9L0 from Dow Chemical and / or polymers such as Synocryl 7013 SD50 from Arkema. Various acrylic monomers can be combined to prepare the acrylic (co)polymers used in this invention. Suitable acrylic monomers may include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyalkyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, allyl methacrylate, isobornyl methacrylate, ethylene glycol dimethacrylate, methacrylic acid, vinyl aromatic compounds (such as styrene and vinyltoluene), nitrile compounds (such as methacrylonitrile), and vinyl esters (such as vinyl acetate). Alternatively, any other acrylic monomer known to those skilled in the art may be used.

[0050] Unless otherwise expressly stated, the terms "acrylic" and "acrylate" are used interchangeably (unless such interchange would alter the intended meaning) and include acrylic acid, acrylic anhydrides, and their derivatives, such as their C1-C5 alkyl esters, lower alkyl-substituted acrylic acids (e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, ethylacrylic acid, etc.) and their C1-C5 alkyl esters. The terms "(meth)acrylic acid" or "(meth)acrylate" are intended to cover the acrylic / acrylate and methacrylic / methacrylate forms of the indicated material, such as (meth)acrylate monomers. The term "acrylic polymer" refers to a polymer prepared from one or more acrylic monomers.

[0051] Suitable film-forming resins may comprise copolymers of polyacrylates and polyester materials. The polyester and acrylate copolymers may be in the form of graft copolymers. Graft copolymers can be formed using standard techniques in the art. In one method, the polyester is prepared using the materials described herein according to conventional methods. An acrylic monomer is then added to the polyester. The acrylic acid can then be polymerized using a standard free radical initiator. In this way, the acrylate copolymer is grafted onto the already prepared polyester. Alternatively, the polyester can be grafted onto a already prepared acrylic copolymer, such as by polymerizing maleic anhydride groups in the acrylic copolymer, and subsequently reacting the hydroxyl groups from the polyester with the acrylic to produce a graft copolymer; the result is an acrylic copolymer having a polyester portion grafted thereon. In the grafting method, the portion to be introduced into the polyester and the monomers to be included with the acrylate monomers that will react with each other are selected. Maleic anhydride can be used to form a polyester and styrene together with the acrylic monomers. The styrene reacts with the maleic anhydride; the acrylic copolymer will grow from the styrene through the formation of free radicals. The result is a polyester having the acrylic copolymer grafted thereon. It should be understood that not all acrylic and polyester will be grafted; therefore, some “pure” polyester and some “pure” acrylate copolymer will be present in the solution. However, sufficient acrylate copolymer and polyester will be grafted to make the two normally incompatible polymers compatible. It should be understood that maleic anhydride and styrene are provided as two suitable components that will promote grafting between normally incompatible polymers, but the copolymer is not limited to this. Other compounds such as fumaric acid / anhydride or itaconic acid / anhydride can be incorporated into the polyester for grafting with styrene-containing acrylic. Other portions that promote grafting between polyester and acrylic can also be used. Any group of the compound can be used for this purpose. All these compounds are referred to herein as “grafting promoters.” The amount of grafting promoter used in each of the polyester and / or acrylate portions can affect the final product. If too much of these components is used, the product may gel or become unusable. Therefore, grafting promoters should be used in an amount that effectively promotes grafting without causing gelling. Sufficient grafting should be performed to make the polyester and acrylate polymers compatible. In maleic anhydride / styrene, 2 to 6% by weight of maleic acid and 8 to 30% by weight of styrene can typically be used, where the weight percentages are based on the weight of the polyester and the weight of the acrylic, respectively.

[0052] Acrylic resins can have any suitable number-average molecular weight (Mn). Acrylic resins may have Mn values ​​of 500 Daltons (Da = g / mole), 10,000 Da, 50,000 Da to 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, or any range using any of the foregoing values ​​as endpoints, such as 500 Da to 250,000 Da, 10,000 Da to 200,000 Da, 50,000 Da to 150,000 Da, 50,000 Da to 100,000 Da. This molecular weight is determined by gel permeation chromatography using polystyrene standards, according to ASTM D6579-11 (Standard Practice for the Determination of Mean Molecular Weight and Molecular Weight Distribution of Hydrocarbon Resins, Rosin Resins and Terpene Resins by Size Exclusion Chromatography, Detector: UV, 254 nm; Solvent: Unstable THF; Retention Time Marker: Toluene; Sample Concentration: 2 mg / ml).

[0053] Acrylic resins may have any suitable weight-average molecular weight (Mw). Acrylic resins may have Mw values ​​of 500 Daltons (Da = g / mole), 10,000 Da, 50,000 Da to 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, or any range using any of the foregoing values ​​as endpoints, such as 500 Da to 250,000 Da, 10,000 Da to 200,000 Da, 50,000 Da to 150,000 Da, 50,000 Da to 100,000 Da, determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11. The weight-average molecular weight (Mw) of the acrylic polymer component may be at least 5,000 Daltons, or 15,000 to 100,000 Daltons.

[0054] Acrylic resins may have any suitable glass transition temperature (Tg). Acrylic resins may have a Tg from -20°C, 0°C, 20°C, 40°C to 60°C, 80°C, 100°C, 120°C, or any range using any of the foregoing values ​​as endpoints, such as -20°C to 120°C, 0°C to 100°C, 20°C to 80°C, or 40°C to 60°C, measured according to ASTM D6604-00 (2013) (“Standard Practice for Determination of Glass Transition Temperature of Hydrocarbon Resins by Differential Scanning Calorimetry”, Heat Flux Differential Scanning Calorimetry (DSC), Sample Pan: Aluminum, Reference: Blank, Calibration: Indium and Mercury, Sample Weight: 10 mg, Heating Rate: 20°C / min).

[0055] Acrylic resins may have any suitable total hydroxyl value (OHV). Acrylic resins may have a total OHV of 0 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g to 150 mg KOH / g, 200 mg KOH / g, 220 mg KOH / g, or any range using any of the foregoing values ​​as endpoints, such as 0 to 220 mg KOH / g, 50 to 200 mg KOH / g, or 100 to 150 mg KOH / g. Total OHV can be expressed in solid form.

[0056] The total hydroxyl value (OHV) of acrylic resins can be measured by any suitable method. Methods for measuring OHV are well known to those skilled in the art. As reported herein, the hydroxyl value is the number of mg of KOH equivalent to 1g of hydroxyl groups in a material. In such methods, a solid acrylic resin sample (typically 0.1 to 3g) is accurately weighed into an Erlenmeyer flask and dissolved in 20 ml of tetrahydrofuran using gentle heating and stirring (as appropriate). Then, 10 ml of 0.1M 4-(dimethylamino)pyridine (catalyst solution) in tetrahydrofuran and 5 ml of a 9% (v / v) solution of acetic anhydride in tetrahydrofuran (i.e., 90 ml of acetic anhydride in 910 ml of tetrahydrofuran; acetylation solution) are added to the mixture. After 5 minutes, 10 ml of an 80% (v / v) solution of tetrahydrofuran (i.e., 4 parts (v / v) of tetrahydrofuran with 1 part (v / v) of distilled water; hydrolysis solution) is added. After 15 minutes, 10 mL of tetrahydrofuran was added, and the solution was titrated with 0.5 M potassium hydroxide ethanol (KOH). A blank sample was also run, in which the solid acrylic resin sample was omitted. The resulting hydroxyl values ​​are expressed in mg KOH / g and calculated using the following formula: Hydroxyl value = (V2 - Vi) × molar concentration of KOH solution (M) × 56.1 / weight of solid sample (g), where Vi is the titer (mL) of KOH solution for the polyester sample, and V2 is the titer (mL) of KOH solution for the blank sample. All values ​​for total hydroxyl value (OHV) reported herein were measured in this manner.

[0057] Acrylic resins can have any suitable acid value (AV). Acrylic resins can have AV values ​​of 0 KOH / g, 25 KOH / g, 50 KOH / g to 100 KOH / g, 125 KOH / g, 150 KOH / g, or any range using any of the foregoing values ​​as endpoints, such as 0 to 150 KOH / g, 25 to 125 KOH / g, or 50 to 100 KOH / g. AV can be expressed in solid form. Those skilled in the art will understand that techniques for measuring number-average molecular weight can also be applied to measuring weight-average molecular weight.

[0058] As reported herein, the acid value (AV) expressed in solid form was determined by titration with 0.1 M methanol-potassium hydroxide (KOH) solution. A solid polymer sample (0.1 to 3 g, depending on the acid number) was accurately weighed into an Erlenmeyer flask and dissolved in 25 mL of dimethylformamide containing phenolphthalein indicator using gentle heating and stirring (as appropriate). The solution was then cooled to room temperature and titrated with 0.1 M methanol-potassium hydroxide solution. The resulting acid number was expressed in mg KOH / g and calculated using the following equation:

[0059] Acid value = titer of KOH solution (ml) × molar concentration of KOH solution (M) × 56.1 / weight of solid sample (g).

[0060] ii. Polyester resin

[0061] Film-forming resins may include polyester resins. Polyester resins may contain reaction products of polybasic acids (or their anhydrides or esters) and polyols.

[0062] As used herein, “polyacid” and similar terms refer to compounds having two or more carboxylic acid groups, such as two, three, or four acid groups, and include polyacid esters (where the acid groups are esterified) or acid anhydrides. Polyacids can be organic polyacids.

[0063] The carboxylic acid group of a polyacid can be linked by a bridging group selected from the following: alkylene; alkenylene; ynylene; or arylene.

[0064] Polyester resins can be formed from any suitable polybasic acid, such as maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; n-sebacic acid; dodecanoic acid; phthalic acid; phthalic anhydride; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; trimellitic anhydride; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methyl hexahydrophthalic acid; dimethyl terephthalate; cyclohexanedicarboxylic acid; chlorobenzyl anhydride; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; tricyclodecane polycarboxylic acid; inner methylene tetrahydrophthalic acid; brined ethyl hexahydrophthalic acid; cyclohexane tetracarboxylic acid; cyclobutane tetracarboxylic acid; esters and / or anhydrides of all the above acids and combinations thereof. The polybasic acid may be selected from phthalic acid, phthalic anhydride, and / or adipic acid. The polybasic acid may be selected from isophthalic acid, terephthalic acid, trimellitic anhydride, and / or adipic acid.

[0065] As used herein, “polyol” and similar terms refer to compounds having two or more hydroxyl groups, such as two, three, or four hydroxyl groups. The hydroxyl groups of a polyol can be linked by bridging groups selected from: alkylene; alkenyl; and ynylene; or aryl. Polyols can be organic polyols.

[0066] Polyester resins can be formed from any suitable polyols, such as alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexanediol; polyethylene glycol; polypropylene glycol and neopentyl glycol; cyclohexanediol; propylene glycol, including 1,2-propanediol; 1,3-propanediol; butyl ethyl propylene glycol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; butanediol, including... Includes 1,4-butanediol; 1,3-butanediol; and 2-ethyl-1,4-butanediol; pentanediol, including trimethylpentanediol and 2-methylpentanediol; cyclohexanediol; hexanediol, including 1,6-hexanediol; caprolactone diol (such as the reaction product of ε-caprolactone with ethylene glycol); polyether diols, such as poly(oxytetramethylene)diol; trimethylolbutane; trimethylolpropane; dimethylolcyclohexane; glycerol, etc., or combinations thereof.

[0067] Polyester resins can be formed from unsaturated polyols, such as trimethylolpropane monoallyl ether; trimethylolethane monoallyl ether; propylene-1-en-1,3-diol or combinations thereof.

[0068] The polyol may be selected from trimethylolpropane and / or neopentyl glycol. The polyol may be neopentyl glycol.

[0069] Polyester resins can be formed from adipic acid, phthalic anhydride and / or phthalic acid, as well as trimethylolpropane and / or neopentyl glycol.

[0070] Polyester resins may contain polymers or copolymers formed by the reaction of diols and diacids; polyol or polyacid components may optionally be used to produce branched polymers.

[0071] Polybasic acids that may be optionally used in the production of branched polymers include, but are not limited to, the following: trimellitic anhydride; trimellitic acid; pyromellitic acid; esters and anhydrides of all the above acids; and mixtures thereof.

[0072] Polyols that may be optionally used in the production of branched polymers include, but are not limited to, the following: glycerol; trimethylolpropane; trimethylolethane; 1,2,6-hexanetriol; pentaerythritol; erythritol; bis(trimethylolpropane); bis(pentaerythritol); N,N,N',N'tetra(hydroxyethyl)hexadiamide; N,N,N'N'tetra(hydroxypropyl)hexadiamide; others, primarily hydroxyl, functional branched monomers; or mixtures thereof.

[0073] Polyester resins can be formed from any suitable molar ratio of polyacid to polyol. The molar ratio of polyacid to polyol in polyester resins can be 20:1, 10:1, 5:1, 2:1 to 1:2, 1:5, 1:10, 1:20, or any range using any of the above ratios as endpoints, such as 20:1 to 1:20, 10:1 to 1:10, 5:1 to 1:5, or 2:1 to 1:2.

[0074] Polyester resins can be formed from any suitable molar ratio of diacid to diol. The molar ratio of diacid to diol in polyester resins can be 10:1, 5:1, 3:1, 2:1 to 1:2, 1:3, 1:5, 1:10, or any range using any of the foregoing ratios as endpoints, such as 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, or 2:1 to 1:2.

[0075] The molar ratio of diacid to diol in polyester resin can be 1.5:1, 1.2:1, 1.1:1 to 1:1.5, 1:1.2, 1:1.1, or any range using any of the aforementioned ratios as endpoints, such as 1.5:1 to 1:1.5, 1.2:1 to 1:1.2, or 1.1:1 to 1:1.1.

[0076] Polyester resins may optionally be formed from any suitable molar ratio of diacid + diol with polyacid and / or polyol. Polyester resins may contain a molar ratio of diacid + diol with polyacid and / or polyol of 100:1. Polyester resins may contain molar ratios of 1:1, 5:1, 20:1 to 50:1, 100:1, or any range using any of the foregoing ratios as endpoints, such as 100:1 to 1:1, 100:1 to 5:1, 100:1 to 20:1, or 100:1 to 50:1 of diacid + diol with polyacid and / or polyol.

[0077] Polyester resins may optionally be formed from additional monomers, such as monobasic acids or monohydric alcohols or combinations thereof. Optional additional monomers may be organic.

[0078] Polyester resins may optionally be formed from an additional monocarboxylic acid. As used herein, "monocarboxylic acid" and similar terms refer to a compound having a carboxylic acid group and include esters (where the acid group is esterified) or anhydrides of the monocarboxylic acid. The monocarboxylic acid may be an organic monocarboxylic acid.

[0079] Polyester resins can optionally be formed from any suitable additional monocarboxylic acid, such as benzoic acid; cyclohexanecarboxylic acid; tricyclodecanecarboxylic acid; camphoric acid; benzoic acid; tert-butylbenzoic acid; C1-C 18 Aliphatic carboxylic acids, such as acetic acid; propionic acid; butyric acid; hexanoic acid; oleic acid; linoleic acid; undecanoic acid; lauric acid; isononanoic acid; fatty acids; hydrogenated fatty acids of naturally occurring oils; esters and / or anhydrides of any of the above acids and combinations thereof.

[0080] Polyester resins may optionally be formed from an additional monohydric alcohol. As used herein, "monohydric alcohol" and similar terms refer to compounds having a single hydroxyl group. Monohydric alcohols may be organic monohydric alcohols.

[0081] Polyester resins may optionally be formed from any suitable additional monohydric alcohol, such as benzyl alcohol; hydroxyethoxybenzene; methanol; ethanol; propanol; butanol; pentanol; hexanol; heptanol; dodecanol; stearyl alcohol; oleyl alcohol; undecyl alcohol; cyclohexanol; phenol; phenyl alcohol; methylphenyl alcohol; cresol; glycol monoether; halogen-substituted or other substituted alcohols and combinations thereof.

[0082] Polyester resins can optionally be formed from any suitable molar ratio of polyacid + polyol:additional monomer. Polyester resins may contain a molar ratio of polyacid + polyol:additional monomer of 100:1. Polyester resins may contain a molar ratio of polyacid + polyol:additional monomer of up to 1:1, such as up to 5:1, such as up to 20:1, or even up to 50:1. Polyester resins may contain a molar ratio of polyacid + polyol:additional monomer of 100:1 to 1:1, such as 100:1 to 5:1, such as 100:1 to 20:1, or even 100:1 to 50:1.

[0083] Polyester resins can be formed from commercially available polyester resins, such as those sold under the trade name URADIL, such as URADIL 250, URADIL 255, URADIL 258, URADIL SZ 260 or URADIL SZ 262, URULAC52260 available from DSM; and those sold under the trade name ITALESTER, such as Italester H 27, Italester H 28, Italester 217 or Italester 218 available from Geistefer Multipolymer Resins; those sold under the trade name IDROBEN, such as IDROBEN 2019, IDROBEN 2026 or IDROBEN 3519 available from Benasedo; or combinations thereof.

[0084] Polyester resins may have any suitable number-average molecular weight (Mn). Polyester resins may have Mn values ​​of 500 Daltons (Da = g / mole), 10,000 Da, 50,000 Da to 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, or any range using any of the foregoing values ​​as endpoints, such as 500 Da to 250,000 Da, 10,000 Da to 200,000 Da, 50,000 Da to 150,000 Da, 50,000 Da to 100,000 Da, determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11.

[0085] Polyester resins may have any suitable weight-average molecular weight (Mw). Polyester resins may have Mw values ​​of 500 Daltons (Da = g / mole), 10,000 Da, 50,000 Da to 100,000 Da, 150,000 Da, 200,000 Da, 250,000 Da, or any range using any of the foregoing values ​​as endpoints, such as 500 Da to 250,000 Da, 10,000 Da to 200,000 Da, 50,000 Da to 150,000 Da, 50,000 Da to 100,000 Da, determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11.

[0086] Polyester resins can have any suitable glass transition temperature (Tg). Polyester resins can have Tgs from -100°C, -75°C, -50°C, -10°C to 10°C, 50°C, 100°C, 120°C, or any range using any of the foregoing values ​​as endpoints, such as -100°C to 120°C, -75°C to 100°C, -50°C to 50°C, or -10°C to 10°C, measured according to ASTM D6604-00 (2013) (“Standard Practice for Determination of Glass Transition Temperature of Hydrocarbon Resins by Differential Scanning Calorimetry”). Heat flux differential scanning calorimetry (DSC), sample pan: aluminum, reference: blank, calibration: indium and mercury, sample weight: 10 mg, heating rate: 20°C / min).

[0087] Polyester resins may have any suitable total hydroxyl value (OHV). Polyester resins may have a total OHV ranging from 0 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g, 110 mg KOH / g to 130 mg KOH / g, 150 mg KOH / g, 190 mg KOH / g, 220 mg KOH / g, or any range using any of the foregoing values ​​as endpoints, such as 0 to 220 mg KOH / g, 50 to 190 mg KOH / g, 100 to 150 mg KOH / g, or 110 to 130 mg KOH / g, measured according to the method described above. Total OHV can be expressed in solid form.

[0088] Polyester resins can have any suitable acid value (AV). Polyester resins can have AV values ​​of 0 KOH / g, 2 KOH / g, 20 KOH / g, 40 KOH / g to 45 KOH / g, 55 KOH / g, 70 KOH / g, 150 KOH / g, or any range using any of the foregoing values ​​as endpoints, such as AV values ​​of 0 to 150 KOH / g, 2 to 70 KOH / g, 20 to 55 KOH / g, or 40 to 45 KOH / g, measured according to the method described above. AV can be expressed in solid form.

[0089] iii. Polyol resins

[0090] Film-forming resins may comprise polyol resins. As used herein, a polyol refers to a polymer having at least two hydroxyl functionalities. The hydroxyl groups may be terminal or present within the polymer chain, or a combination thereof. The polymer backbone may contain additional functionalities, such as polyethers, polyesters, polyurethanes, or any combination thereof. The polymer backbone may be linear or branched. Suitable polyol resins include polyethylene glycol bisphenol-A, commercially available resins such as Ingevity Capa 2043, Ingevity Capa 2100, Ingevity Capa 3301, Ingevity Capa 3031 (available from Ingenvix), JEFFOL PPG-400, JEFFOF PPG-1000, JEFFOF PPG-2000, JEFFOF PPG-2801, JEFFOF PPG-3703, JEFFOF PPG-3706, JEFFOF PPG-3709, JEFFOF FC31-56, JEFFOF G31-43 (available from Huntsman), Pluracol 1010, Pluracol 2010, Pluracol 628, Pluracol 1016, Pluracol 1158, Pluracol 2100, and Pluracol... 380, Pluracol 1168, Pluracol 736 (available from BASF), VORANOF 6150 polyol, VORANOF 2000FM polyol, VORANOF 1000FM polyol, VORANOF 8136 polyol, VORANOF CP 6055 (available from DOW), Fupraphen 1602 / 1, Fupraphen 1608 / 2, Fupraphen 2605 / 1 (available from BASF), DESMOPEN 1800, DESMOPEN 1200, DESMOPEN 670 BA, DESMOPEN 2060 BD, DESMOPEN C 1200 (available from Covestro).

[0091] iv. Polyurethane resin

[0092] Film-forming resins may include polyurethane resins. As used herein, polyurethane refers to a polymer having two or more urethane bonds in its main chain. Terminal functionalities may include hydroxyl, acid, and / or amine functionalities. Polyurethane resins may also contain cofunctionalities in the polymer main chain, such as polyester and / or polyether functionalities. Suitable polyurethane resins include DAOTANTW 642540WA, DAOTAN TW 6450 / 30WA, DAOTAN VTW 1225 / 40WA (available from Zhanxin), BAYBOND PU330, BAYBOND PU 401A, BAYCUSAN C 1000 / 1, BAYCUSAN C 1010, BAYHYDROL U 2698, BAYHYDROL U 2750, DESMCOLL 176, DESMCOLL 400 / 1, DESMOLAC 2100 (available from Covestro), NEOREZ U-371, NEOREZ U-397, and URAFLEX EU220 ML (available from DSM).

[0093] v. Epoxy resin

[0094] Film-forming resins may include epoxy resins. As used herein, epoxy resins are polymers having two or more epoxy, ethylene oxide, and / or glycidyl ether functional groups. The epoxy functional groups may be located at the ends of the polymer backbone or contained within substructures of the polymer backbone. Epoxy resins may be formed from bisphenols, alicyclic compounds, or derivatives thereof. Suitable components for forming epoxy resins include DER™ 331, DER™ 351, DER™ 354, DER™ 3572, DER™ 915, DER™ 900, DEN™ 425, DEN™ 431 (available from DOW), ARALDITE GY 260, ARALDITE GY 240, ARALDITE PY 306, ARALDITE ECN 1400 (available from Huntsman), EPI-REZ Resin WD-510, EPI-REZ Resin 7510-W-60, EPON Resin 828, and EPON Resin 869 (available from Huntsman).

[0095] B. Crosslinking materials

[0096] The topcoat composition may further include crosslinking materials.

[0097] Crosslinking materials may contain chemical groups suitable for crosslinking into film-forming resins. Crosslinking materials may contain: phenolic groups, melamine groups, hydroxyl-substituted aromatic groups; isocyanate groups; amino groups; amine groups; urea-formaldehyde and / or alkyl urea with imino functionality. Crosslinking materials may contain amino groups. Crosslinking materials may be in the form of monomers, dimers, oligomers, (co)polymers, or mixtures thereof.

[0098] Suitable isocyanate-containing crosslinking materials may include IPDI (isophorone diisocyanate), such as DESMODURVP-LS 2078 / 2 or DESMODUR PL 340 (DESMODUR crosslinker, available from Covestro) or VESTANAT B 1370 or VESTANAT B1358A (VESTANAT crosslinker, available from Evonik Industries) or HDI-based capped aliphatic polyisocyanates such as DESMODUR BL3370 or DESMODUR BL 3175 SN (available from Covestro) or DURANATE MF-K60X (available from Asahi Kasei) or TOLONATE D2 (available from Concord) and / or TRIXENE-BI-7984 or TRIXENE7981 (available from Asahi Kasei).

[0099] Suitable water-dilutable isocyanate crosslinking materials may include BAYHYDUR BL2781, BAYHYDUR BL5140, BAYHYDUR 2655 (available from Covestro), AQUALINK X and / or AQUALINK U-HT (available from AQUALINK Dispersions).

[0100] Suitable amino-containing crosslinking materials may include hexa(methoxymethyl)melamine (HMMM) type melamine-formaldehyde materials, such as KOMELOL 90GE (available from Meramine), MAPRENAL MF900 (available from Preferre Resin Holdings Limited), or RESIMENE 745 or RESIMENE 747 (available from Preferre Resin Holdings Limited), or CYMEL 303 and / or CYMEL MM100 (available from Zhanxin). Other melamine-formaldehyde materials, such as butylated hydroxymethyl melamine resins, such as CYMEL 1156 or CYMEL 1158 (available from Zhanxin), or mixed ether methyl acetal melamine resins, such as CYMEL 1116, CYMEL 1130, CYMEL 1133, or CYMEL 1168 (available from Zhanxin), or partially hydroxymethylated and partially methylated melamine resins, such as CYMEL 370, CYMEL 325, or CYMEL327 (available from Zhanxin).

[0101] Other suitable types of amino-based crosslinking materials may include benzoguanamine formaldehyde-based materials, such as CYMEL 1123 (available from ZNX), ITAMIN BG143 (available from Geistefer Multi-Resin Company), or MAPRENAL (Uramex) BF891 and / or MAPRENAL BF892 (available from Preferell). Additionally, suitable amino-based crosslinking agents include glycourea-based materials, such as CYMEL 1170 and CYMEL 1172 (available from ZNX).

[0102] Suitable urea-formaldehyde crosslinking materials may include CYMEL U-80 or CYMEL U-60 (available from Zhanxin), MAPRENAL UF 264 (available from Preferre), ASTRO SET 90 (available from Momentive), CURAZINE 42-316 or CURAZINE 42-338 or CURAZINE 42-360 or CURAZINE 42-365 or CURAZINE 42-367 and / or CURAZINE 42-378 (available from Bitrez).

[0103] Suitable amine-containing crosslinking materials may include triethylenetetramine (available from Dow), ARADUR 115 BD, 125 BD, 140 BD (available from Huntsman), dicyandiamide (available from Azken), and / or CASAMID DMPFF.

[0104] The varnish composition may contain 10 wt.%, 15 wt.%, 20 wt.% to 25 wt.%, 30 wt.%, 35 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 10 wt.% to 35 wt.%, 15 wt.% to 30 wt.%, or 20 wt.% to 25 wt.%, of crosslinked material, wherein wt.% is based on the total “wet” weight of the varnish composition.

[0105] The topcoat layer may contain 20 wt.%, 22 wt.%, 24 wt.% to 26 wt.%, 30 wt.%, 35 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 20 wt.% to 35 wt.%, 22 wt.% to 30 wt.%, or 24 wt.% to 26 wt.%, of crosslinked material, where wt.% is based on the total “dry” weight of the topcoat layer.

[0106] C. Lubricant

[0107] The topcoat composition may contain a lubricant. The lubricant may be such as microcrystalline wax, polyethylene wax, carnauba wax, lanolin wax, Fischer-Tropsch wax, paraffin wax, castor wax, polypropylene wax, bio-wax and / or amide derivatives of the former.

[0108] The varnish composition may contain 0.1 wt.%, 0.5 wt.%, 1 wt.% to 1.5 wt.%, 2 wt.%, 3 wt.%, or any range including any two of these values ​​as endpoints, such as 0.1 wt.% to 3 wt.%, 0.5 wt.% to 2 wt.%, or 1 wt.% to 1.5 wt.%, of which wt.% is based on the total “wet” weight of the varnish composition.

[0109] The topcoat layer may contain 0.5 wt.%, 0.7 wt.%, 1 wt.% to 1.2 wt.%, 1.5 wt.%, 2 wt.%, or any range including any two of these values ​​as endpoints, such as 0.5 wt.% to 2 wt.%, 0.7 wt.% to 1.5 wt.%, or 1 wt.% to 1.2 wt.%, of which wt.% is based on the total “dry” weight of the topcoat layer.

[0110] D. Organosilicon-modified polymers

[0111] The topcoat composition may contain silicone copolymers, such as silicone-modified polymers. These silicone-modified polymers can be organosiloxane-based polymers, such as methyl silicone resins, phenyl silicone resins, or methyl-phenyl silicone resins, which are typically thermosetting compositions capable of providing a range of mechanical properties. The silicone-modified copolymer can affect the surface energy of the topcoat composition, allowing it to possess desiccant properties that enable the composition to wick away from the tactile or other textured surfaces of the coated substrate. The silicone-modified copolymer can maintain the mesh-like effect of the tactile topcoat.

[0112] To form organosilicon-modified polymers, organosilicon-containing polymers (such as organoalkoxysiloxanes) can be hydrolyzed or grafted onto hydrophobic polymers (such as acrylic, epoxy, polyurethane, or polyester polymers).

[0113] Exemplary organoalkoxysilanes have the following formula:

[0114] RxSi(OR')4-x

[0115] Wherein R is one or more moieties independently selected from straight-chain, branched or cyclic alkyl and aryl (including cyclohexyl and / or phenyl); R' is methyl, ethyl, propyl or alkyl; and x is 0, 1, 2 or 3.

[0116] The degree of crosslinking, in turn, depends on the nature of the organosiloxane unit used in the composition. As shown in Table A below, organosiloxanes can be described according to the degree of oxygen substitution or functionality on the central silicone.

[0117] Table A: Oxygen Substitution of Organosiloxanes

[0118]

[0119] Typically, compositions containing higher-order T (trifunctional) and Q (tetrafunctional) units exhibit higher crosslinking degrees.

[0120] R is a C6 aryl group or a straight-chain or branched alkyl group having 1, 2, 3 or 4, 5, 6 or more carbon atoms, or any other combination of these endpoints. R may be selected from methyl, ethyl, propyl, and phenyl. X may be at least 1 and less than 4.

[0121] Organosilicon polymers can be hydrolyzed to form silicone-modified polymers containing at least one organoalkoxysilane residue selected from methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, or combinations thereof.

[0122] The organoalkoxysilane can be a functionalized siloxane, such as 3-aminopropyltriethoxysilane, (3-glycidyl etheroxypropyl)trimethoxysilane, and allyltrimethoxysilane. A suitable organoalkoxysilane is RSN-5314 resin, available from Dow Corning of Midland, MI.

[0123] Other suitable organosilicon materials are silsesquioxanes with the following formula:

[0124] [RSiO3 / 2] n

[0125] Where R = H, alkyl, aryl, or alkoxy; and n equals the number of repeating units in sesquioxane.

[0126] The topcoat composition may contain 0.05 wt.%, 0.1 wt.%, 0.5 wt.% to 1 wt.%, 1.25 wt.%, 1.5 wt.%, or any range including any two of these values ​​as endpoints, such as 0.05 wt.% to 1.5 wt.%, 0.1 wt.% to 1.25 wt.%, or 0.5 wt.% to 1 wt.%, of a silicone-modified polymer, wherein wt.% is based on the total “wet” weight of the topcoat composition.

[0127] The topcoat layer may contain 0.00 wt.%, 0.03 wt.%, 0.05 wt.% to 0.07 wt.%, 0.10 wt.%, 0.15 wt.%, or any range including any two of these values ​​as endpoints, such as 0.00 wt.% to 0.15 wt.%, 0.03 wt.% to 0.10 wt.%, or 0.05 wt.% to 0.07 wt.%, of a silicone-modified polymer, where wt.% is based on the total “dry” weight of the topcoat layer.

[0128] E. Precipitated silica

[0129] The topcoat composition may contain precipitated silica. Precipitated silica can be a solid material produced by precipitation from a sodium silicate solution. Precipitated silica is a synthetic amorphous form of silica derived from quartz sand, which can increase the surface area of ​​the topcoat composition and reduce the coefficient of friction. Similar to silicone-modified copolymers, the topcoat composition may have desiccant properties that allow the composition to wick away from tactile or other textured surfaces of the substrate. Precipitated silica may be necessary because its high surface area and oil-absorbing properties can attract hydrophobic polymers, such as silicone-modified copolymers. As a result, a discontinuous silicone phase may form, leading to the migration of Fischer-Tropsch wax to the coating surface. The presence of Fischer-Tropsch wax on the coating surface may also contribute to a reduced coefficient of friction.

[0130] The topcoat composition may contain 0.1 wt.%, 0.2 wt.%, 0.5 wt.% to 1 wt.%, 1.5 wt.%, 2 wt.%, or any range including any two of these values ​​as endpoints, such as 0.1 wt.% to 2 wt.%, 0.2 wt.% to 1.5 wt.%, or 0.5 wt.% to 1 wt.%, of precipitated silica, where wt.% is based on the total “wet” weight of the topcoat composition.

[0131] The topcoat layer may contain 0.00 wt.%, 0.05 wt.%, 0.10 wt.% to 0.15 wt.%, 0.20 wt.%, 0.30 wt.%, or any range including any two of these values ​​as endpoints, such as 0.00 wt.% to 0.30 wt.%, 0.05 wt.% to 0.20 wt.%, or 0.10 wt.% to 0.15 wt.%, of precipitated silica, where wt.% is based on the total “dry” weight of the topcoat layer.

[0132] F. Catalyst

[0133] The clear coat composition may further comprise a catalyst. Any catalyst commonly used for catalyzing crosslinking reactions between film-forming resins and / or between film-forming resins and crosslinking materials can be used. Suitable catalysts are well known to those skilled in the art. The catalyst may be a nonmetallic or metallic catalyst or a combination thereof. Suitable nonmetallic catalysts include, but are not limited to, the following: phosphoric acid; terminally capped phosphoric acid; phosphating resins, such as phosphating epoxy resins and phosphating acrylic resins; CYCAT (RTM)XK 406 N (available from ZN); sulfuric acid; sulfonic acid; CYCAT 600 (available from ZN); NACURE (RTM) 155 or NACURE 2500 (available from King's Industries); NACURE (RTM) 5076 or NACURE 5925 (available from King's Industries); phenyl phosphate catalysts; phosphate catalysts, such as NACURE XC 235 (available from King's Industries); p-toluenesulfonic acid, such as NACURE 2547 (available from King's Industries); and combinations thereof.

[0134] Suitable metal catalysts are well known to those skilled in the art. Suitable metal catalysts include, but are not limited to, the following: tin-containing catalysts, such as tris(2-ethylhexanoic acid) monobutyltin; zirconium-containing catalysts, such as KKAT (RTM) 4205 (available from King's Industries); titanate-based catalysts, such as tetrabutyl titanate TnBT (available from Sigma-Aldrich); and combinations thereof.

[0135] The varnish composition may contain 0.001 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.% to 1 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 10 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 0.001 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.05 wt.% to 3 wt.%, 0.1 wt.% to 2 wt.%, or 0.2 wt.% to 1 wt.%, of a catalyst, wherein wt.% is based on the total “wet” weight of the varnish composition.

[0136] G. Solvent

[0137] The topcoat composition may contain a solvent and may be an aqueous or solvent-based composition.

[0138] When the topcoat composition is an aqueous composition, the composition may contain water as a solvent, such that the majority of the solvent in the topcoat composition is water, meaning that based on the total “wet” weight of the topcoat composition, the topcoat composition contains less than 20 wt.% organic (i.e., non-aqueous) solvent.

[0139] When the topcoat composition is an aqueous composition, the composition may contain a solvent in which the majority of the solvent is water, or, based on the total weight of the solvent in the topcoat composition, the solvent contains less than 35 wt.% organic (i.e., non-aqueous) solvent.

[0140] When the topcoat composition is solvent-based, the composition may contain organic (i.e., non-aqueous) solvents, such that most of the solvent in the topcoat composition is an organic solvent, meaning that the topcoat composition contains less than 10 wt.% water based on the total “wet” content of the topcoat composition.

[0141] Suitable organic solvents may include alcohols, esters, ketones, glycols, glycol ethers, glycol ether esters, aromatic hydrocarbons, aliphatic hydrocarbons and / or their derivatives, such as diethylene glycol monobutyl ether, di(propylene glycol)methyl ether, 2-butoxyethanol, xylene, toluene, Aromatic Solvent 100, Aromatic Solvent 150, ethyl butoxyacetate, ethyl 2-(2-butoxyethoxy)acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, n-butanol, isobutanol, 1-methoxy-2-propyl acetate, n-propanol, cyclohexanone, cyclopentanone, methyl isobutyl ketone and / or 2-butanone.

[0142] The topcoat composition may contain 20 wt.%, 25 wt.%, 30 wt.% to 40 wt.%, 50 wt.%, 60 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 20 wt.% to 60 wt.%, 25 wt.% to 50 wt.%, 30 wt.% to 40 wt.%, where wt.% is based on the “wet” weight of the topcoat composition.

[0143] H. Additives

[0144] The clear coat composition may also contain one or more additives, such as tackifiers, plasticizers, surfactants, flow control agents, defoamers, thixotropic agents, fillers, diluents, organic solvents, slip agents such as BYK-333, wetting agents, fluorescent whitening agents, stabilizers, and / or odor masking agents. The clear coat composition may also contain other optional additives known in the field of coating formulation, such as matting agents, leveling agents, plasticizers, abrasion-resistant particles, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, abrasive carriers, and / or other conventional additives.

[0145] The varnish composition may contain additives in amounts of 0.001 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 2 wt.% to 3 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 0.001 wt.% to 20 wt.%, 0.01 wt.% to 15 wt.%, 0.05 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, or 2 wt.% to 3 wt.%, where wt.% is based on the “wet” weight of the varnish composition.

[0146] The topcoat layer may contain additives in amounts of 0.45 wt.%, 0.50 wt.%, 0.55 wt.% to 1.00 wt.%, 1.10 wt.%, 1.50 wt.%, or any range including any of the foregoing values ​​as endpoints, such as 0.45 wt.% to 1.50 wt.%, 0.50 wt.% to 1.10 wt.%, 0.55 wt.% to 1.00 wt.%, where wt.% is based on the “dry” weight of the topcoat layer.

[0147] III. Application of the Topcoat Composition

[0148] A. Substrate

[0149] A clear coat composition can be applied to a substrate, such as a metal substrate, such that at least a portion of the substrate is coated with the clear coat composition and cured to form a clear coat layer on the surface of the substrate. A method for applying and curing a clear coat composition to a substrate is described below.

[0150] Suitable metal substrates include, but are not limited to, food and / or beverage packaging, components for manufacturing such packaging, and monolithic aerosol cans and / or tubes.

[0151] Food and / or beverage packaging may be cans. Cans may include, but are not limited to, two-piece cans, three-piece cans, etc. Food and / or beverage packaging may be two-piece metal cans. Suitable single-piece aerosol cans and / or tubes include, but are not limited to, deodorant containers and hairspray containers. Single-piece aerosol cans and / or tubes may be aluminum single-piece aerosol cans and / or tubes.

[0152] The substrate can be packaging at least partially coated with any of the coating compositions described herein. “Packaging” is any substance intended to contain another article, particularly for transport from the point of manufacture to the consumer, and subsequently stored by the consumer. Therefore, packaging will be understood as a substance sealed to prevent its contents from spoiling before being opened by the consumer. Manufacturers typically determine the length of time during which food or beverages will not spoil, usually ranging from several months to several years. Therefore, the “packaging” of this invention differs from storage containers or baking pans in which consumers can prepare and / or store food; such containers only maintain the freshness or integrity of food for a relatively short period. Packaging can be made of metal or non-metallic plastic or laminated materials and can be of any form. Suitable packaging may be laminated tubing. Another suitable packaging may be a metal can.

[0153] The term "metal can" encompasses any type of metal can, container, or reservoir, or part thereof, sealed by food and / or beverage manufacturers to minimize or eliminate spoilage of the contents before a consumer opens such packaging. A suitable metal can may be a food can; the term "food can" is used herein to refer to a can, container, or reservoir, or part thereof, used to contain any type of food and / or beverage. The term "metal can" specifically includes food cans and also specifically includes a "can end" comprising an "EZ opening," which is typically stamped from cap end material and used in conjunction with food and beverage packaging. The term "metal can" also specifically includes metal caps and / or closures, such as bottle caps, screw-top caps, and caps of any size, snap-on caps, etc. Metal cans may also be used to hold other items, including but not limited to personal care products, pesticides, paints, and any other compounds suitable for packaging in aerosol cans. Cans may include "two-piece cans" and "three-piece cans," as well as pull-out and iron-on integrated cans; such integrated cans are frequently used for aerosol products.

[0154] B. Application method

[0155] The topcoat composition can be applied to food and / or beverage packaging by any means known in the art. Application methods suitable for the topcoat compositions of this disclosure include, but are not limited to, electrophoretic coating (such as electrodeposition), spraying, electrostatic spraying, dip coating, roller coating, brush coating, lamination, etc.

[0156] A topcoat composition can be applied such that the dry film thickness of the topcoat composition is 0.5 micrometers (μm), 1 μm, 2 μm, 4 μm to 10 μm, 15 μm, 20 μm, 25 μm, or any range such as 0.5 μm to 25 μm, 1 μm to 20 μm, 2 μm to 15 μm, or 4 μm to 10 μm, using any of the foregoing values ​​as endpoints, as determined by an electronic measuring instrument.

[0157] The clear coat composition can be applied to a substrate by roller coating. Therefore, the clear coat composition can be a roller-coated composition. For the avoidance of doubt, the term "roller-coated composition" and similar terms used herein, unless otherwise stated, refer to a composition suitable for application to a substrate by roller coating, i.e., capable of roller coating.

[0158] The clear coat composition can be applied to a substrate by spraying. Therefore, the clear coat composition can be a sprayable composition. For the avoidance of doubt, unless otherwise stated, as used herein, the term "sprayable composition" and similar terms mean that the composition is suitable for application to a substrate by spraying, i.e., it is sprayable.

[0159] The clear coat composition can be applied as a single layer or as part of a multilayer system to a substrate or a portion thereof. The clear coat composition can be applied as a single layer, forming a clear coat layer. The clear coat composition can be applied to an uncoated substrate. For the avoidance of doubt, the uncoated substrate extends to a clean surface prior to application. The clear coat composition can be applied as part of a multilayer system over another paint layer. The clear coat composition can be applied over a primer or intermediate coat. The clear coat composition can form a topcoat layer (clear coat layer).

[0160] The topcoat composition can be applied to the substrate in one or more coats.

[0161] Various pretreatments and coatings are well-established for application to substrates such as single-piece aerosol cans. These treatments and / or coatings can be used to provide decorative coatings. Topcoat compositions can form a topcoat layer on top of the decorative coating to protect it from abrasion and / or damage. The topcoat layer can also provide a decorative gloss finish. Topcoat compositions can be applied to the exterior of food and / or beverage cans.

[0162] The substrate can be coated with a topcoat composition onto at least a portion of its outer surface.

[0163] C. Curing

[0164] After application, the coating will be cured. Curing the coating composition can form a cured film.

[0165] The coating composition can be cured by any suitable method. The coating composition can be cured by heat curing, radiation curing, or chemical curing, such as by heat curing. When heat curing, the coating composition can be cured at any suitable temperature. The clear coat composition can be cured by heat curing, i.e., by heating to 80°C, 120°C, 160°C to 180°C, 220°C, 250°C, or any range with any two of these values ​​as endpoints, such as 80°C to 250°C, 120°C to 220°C, or 160°C to 180°C.

[0166] When thermosetting, the coating composition can be cured at temperatures from 210°C to 260°C. If another layer is applied to the substrate after the clear coat layer described herein, the other layer may comprise a coating composition that can be thermoset at temperatures up to 250°C, such as 80 to 250°C.

[0167] Unless otherwise stated, the term "peak metal temperature" and similar terms as used herein refer to the highest temperature reached by a metal substrate when heated during the thermosetting process. In other words, the peak metal temperature (PMT) is the highest temperature reached by the metal substrate, not the temperature applied to it. Those skilled in the art will understand that the temperature reached by the metal substrate may be lower than the temperature applied to it, or may be substantially equal to the temperature applied to it. The temperature reached by the metal substrate may be lower than the temperature applied to it.

[0168] Thermosetting can be performed in one or more cycles. The coating can undergo two curing cycles, in which the curing temperature and duration can be the same or different. Thermosetting in each cycle can be performed independently for 1 minute, 2 minutes, 3 minutes, 4 to 5 to 7 minutes, 8 minutes, 10 minutes, or any range such as 1 to 10 minutes, 2 to 8 minutes, 3 to 7 minutes, or 4 to 5 minutes, using any of the foregoing values ​​as endpoints.

[0169] IV. Properties of the Topcoat Layer

[0170] A. Free of perfluorinated and polyfluorinated substances (PFAS)

[0171] The topcoat composition may be substantially free of, such as substantially free of or completely free of, perfluorinated and polyfluorinated substances (PFAS) and their derivatives. Perfluorinated and polyfluoroalkyl substances (PFAS) are fluorinated compounds, including perfluoroalkyl acids (PFAAs), such as perfluorooctanoic acid (PFOA) and / or perfluorooctane sulfonate (PFOS). PFOA derivatives include polytetrafluoroethylene (PTFE). Therefore, the topcoat composition may be substantially free of, such as substantially free of or completely free of PTFE. It is desirable to reduce the level of perfluorooctanoic acid (PFOA) because PFOA is considered carcinogenic and has been linked to cancer and harm to unborn infants, making it necessary to prevent and / or reduce its use in coatings.

[0172] As used herein, “substantially free” in relation to PFAS and their derivatives means that the varnish composition (and varnish layers derived therefrom) contains less than 1,000 parts per million (ppm) of PFAS and their derivatives. As used herein, “substantially free” means that the varnish composition (and varnish layers derived therefrom) contains less than 100 ppm of PFAS and their derivatives. As used herein, “completely free” means that the varnish composition (and varnish layers derived therefrom) contains less than 20 parts per billion (ppb) of PFAS and their derivatives.

[0173] B. BPA-free

[0174] The composition may be substantially free of, substantially free of, or completely free of bisphenol A and its derivatives or residues, including bisphenol A (“BPA”) and bisphenol A diglycidyl ether (“BADGE”). Such compositions are sometimes referred to as “unintentional BPA” because BPA, including its derivatives or residues, is not intentionally added but may be present in trace amounts due to unavoidable environmental contamination. The composition may also be substantially free of, substantially free of, or completely free of bisphenol F and its derivatives or residues, including bisphenol F and bisphenol F diglycidyl ether (“BPFG”). As used herein, “substantially free” means that the composition or resulting coating contains less than 1,000 ppm of any of the above-mentioned compounds, their derivatives, or residues, “substantially free” means less than 100 ppm, and “completely free” means less than 20 ppb.

[0175] C. Free of dialkyltin

[0176] The coating composition may be substantially free of, substantially free of, or completely free of dialkyltin compounds, including their oxides or other derivatives. Suitable dialkyltin compounds include, but are not limited to, the following compounds: dibutyltin dilaurate (DBTDF); dioctyltin dilaurate; dimethyltin oxide; diethyltin oxide; dipropyltin oxide; dibutyltin oxide (DBTO); dioctyltin oxide (DOTO); or combinations thereof. As used herein, “substantially free of” means that the composition or resulting coating contains less than 1,000 ppm of any of the above compounds, their derivatives, or residues; “substantially free of” means less than 100 ppm; and “completely free of” means less than 20 ppm.

[0177] D. Styrene-free

[0178] The topcoat composition may be substantially styrene-free. The coating composition may be substantially styrene-free or may be completely styrene-free. As used herein, “substantially styrene-free” means that the composition or resulting coating contains less than 1,000 ppm of any of the above-mentioned compounds, their derivatives or residues, “substantially styrene-free” means less than 100 ppm and “completely styrene-free” means less than 20 ppm.

[0179] E. Phenol-free

[0180] The topcoat composition may be substantially free of phenol, or substantially free of phenol, or completely free of phenol. As used herein, “substantially free of phenol” means that the composition or resulting coating contains less than 1,000 ppm of any of the above-mentioned compounds, their derivatives or residues, “substantially free of phenol” means less than 100 ppm and “completely free of phenol” means less than 20 ppm.

[0181] D. Formaldehyde-free

[0182] The topcoat composition may be substantially formaldehyde-free, substantially formaldehyde-free, or completely formaldehyde-free. As used herein, “substantially formaldehyde-free” means that the composition or resulting coating contains less than 1,000 ppm of any of the aforementioned compounds, their derivatives, or residues, “substantially formaldehyde-free” means less than 100 ppm, and “completely formaldehyde-free” means less than 20 ppm.

[0183] Example

[0184] The various aspects of this disclosure will be further illustrated with reference to the following examples. It will be apparent to those skilled in the art that many modifications can be made to the materials and methods without departing from the scope of this disclosure.

[0185] Test methods

[0186] AGR / CQF (Coefficient of Friction) of the Tilted Table Filling Tank

[0187] The test uses an AGR tilt table lubrication tester and two filled beverage cans. Two cans are placed sideways on the base plate of the tester, and a slide bar is used to push the cans together. A third, full can is then placed sideways on top of the first two cans, forming a pyramid. The AGR tilt table is turned on, and the base plate begins to tilt upwards. The top can eventually slide off the two lower cans and hit a stop plate. The angle at which this occurs is recorded.

[0188] Altek directly CQF

[0189] This test uses an Altek 9505DAF1C flowability / lubricity tester and a coated panel prepared at least 3 inches by 6 inches and properly baked. A 2-inch wide section of the panel is cut off and reserved for the Altek face-to-face test. A 2 kg weight with three ball bearings is placed on the now 2-inch by 4-inch panel and attached to a pull hook. The equipment is turned on, and the weight is pulled at a speed of 5 inches per minute to generate the average direct coefficient of friction.

[0190] Altek Face-to-Face CQF

[0191] This test uses an Altek 9505DAF1C flowability / lubricity tester and a coated panel prepared at least 3 inches by 6 inches with an appropriate baking cycle. A 2-inch wide section of the panel is cut off and placed on top of the larger panel, with the two coated sides in contact. A 2 kg weight (with three felt-covered ball bearings) is placed on top of the smaller, face-down panel and attached to a pull hook. The equipment is turned on, and the weight is pulled at a speed of 5 inches per minute to generate an average face-to-face coefficient of friction.

[0192] MEK dual friction

[0193] The test method used is similar to ASTM D5402, but a 2-pound round-headed hammer is used instead of a human hand. A 4x4, 12-layer piece of gauze is placed on the ball end of the 2-pound round-headed hammer and secured with a rubber band. The gauze is then soaked in methyl ethyl ketone (MEK) and rubbed against the test plate using a back-and-forth motion. Each back-and-forth motion is counted as one "double rub," and this motion continues until the bare substrate is exposed at the center of the strip where the rub is performed.

[0194] Pencil hardness

[0195] The pencil hardness of the topcoat can be tested using ASTM D3363.

[0196] TQCAT testing method

[0197] Six cleaned, sewn, and filled cans are secured together to form a six-can pack. The six-can pack is placed in a TQCAT instrument, which applies pressure to the top and sides of the pack. The cans are shaken back and forth for 10 minutes to simulate transport abrasion. The cans are graded based on the amount of damage perceived along the abrasion points, ranging from no perceptible damage to complete metal failure where the can may leak. This process is repeated for a total of 60 minutes, or until a can leaks within the pack. After the test is completed, a total score is calculated based on each 10-minute grading cycle.

[0198] Tribometer wear test method for coated substrate

[0199] The abrasion resistance of the coating was tested using the following method with a coated substrate and steel balls. The coating composition was applied to the substrate by scraping or spraying. After application, the coated substrate was first flash-dried at 204°C for 1 minute, then cured at 204°C for 3 minutes. The dry film thickness was 2 to 5 micrometers. The balls and coated substrate were then tested using a Bruker UMT-3 tribometer according to the ASTM G99 disc-ball wear test protocol. The steel balls had a diameter of 6.35 mm. The coated substrate was mounted on a lower rotary drive. Tests were performed at a load of 10 N and 240 rpm until the coefficient of friction was greater than 0.5. Each test was repeated 2 to 3 times and the average was reported. The trend of the coefficient of friction and visible track wear were evaluated.

[0200] Differential scanning calorimetry (DSC)

[0201] Thermal properties of waxes, such as melting temperature and enthalpy of fusion, were measured using a DISCOVERY DSC 2500 instrument. DSC experiments involved hot-cold-hot cycling of approximately 3 to 5 mg of wax sealed in a Tzero aluminum disc. The temperature range for non-fluorinated waxes was -90°C to 220°C, and for fluorinated waxes, it was -90°C to 350°C. The heating / cooling rate was 10°C / min.

[0202] Example 1:

[0203] Preparation of acrylic resin

[0204] Acrylic resins with different glass transition temperatures (Tg) as shown in Table 1 were prepared according to the following procedure (amounts are given as a percentage by weight):

[0205] 1. Add feed #1 to the round-bottom reaction flask. Turn on the cooling water and nitrogen protection. Heat the mixture to 320-325℉, with a temperature setpoint of 323℉.

[0206] 2. The batch temperature is 320-325℉. Add feed #2 and 67.07% of feed #3 within 180 minutes.

[0207] 3. After feeding is complete, add rinsing feed #4. Keep the batch for 15 minutes.

[0208] 4. After holding the position, add 32.93% of feed #3 within 20 minutes.

[0209] 5. When feeding material #3 is complete, add rinsing material #6. Keep the batch for 30 minutes.

[0210] 6. After holding, lower the batch set point to 180℉.

[0211] 7. Once the batch temperature drops below 240℉, add feed #7.

[0212] 8. Once feeding #7 is complete, add feeding #8 within 45 minutes. 9. Once feeding #8 is complete, allow for complete cooling. Add more deionized water if necessary to achieve the desired viscosity.

[0213] Table 1: Acrylic resins with different Tg

[0214]

[0215] Preparation of acrylic acid

[0216] Prepare the acrylic resin shown in Table 2 according to the following procedure (amounts are given as a weight percentage based on the total weight of the topcoat composition):

[0217] 1. Add feed #1 to the round-bottom reaction flask. Turn on the cooling water and nitrogen protection. Heat the mixture to 275-290℉, with a temperature setpoint of 286℉.

[0218] 2. The batch temperature is 275-280℉. Add feed #2 and 86.75% of feed #3 within 180 minutes.

[0219] 3. After feeding is complete, add rinsing feed #4. Keep the batch for 15 minutes.

[0220] 4. After holding the feed in place, add 13.25% of feed #3 within 10 minutes.

[0221] 5. Once feeding #3 is complete, keep the batch for 90 minutes.

[0222] 6. After holding, lower the batch setpoint to 205℉.

[0223] 7. When the batch temperature reaches 205℉, add feed #5.

[0224] 8. When feeding #5 is complete, hold the batch for 30 minutes. During this holding period, preheat feeding #6 to 160℉.

[0225] 9. After holding, lower the temperature setpoint to 160℉ and add preheated feed #6 within 25 minutes.

[0226] 10. After feeding #6 is completed, keep the batch for 120 minutes, then allow it to cool completely to room temperature.

[0227] Table 2: Resins

[0228]

[0229] Preparation of water-based topcoat composition

[0230] The topcoat compositions in Tables 3 and 4 are prepared as follows (amounts are given as a percentage by weight):

[0231] 1. Add dimethylethanolamine and butyl cellosolve (if present) to the acrylic resin (prepared as above). Stir the mixture at medium speed for 1 minute at room temperature using a laboratory mixer.

[0232] 2. Then add BPA polyol and CYMEL 303 LF into the container and stir at medium speed for another 2 to 3 minutes.

[0233] 3. The tackifier, BYK-333, catalyst, and MAGIESOL 52 were added separately during low-speed constant stirring.

[0234] 4. Prepare a wax dispersion containing acrylic acid, wax, and water in a separate container. Using a laboratory mixer, stir the acrylic acid at medium shear and slowly add the wax. Once the wax is fully incorporated, stir the mixture at high shear for 10 minutes. Reduce the stirring speed and add water to reduce dispersion.

[0235] 5. Add the freshly prepared wax dispersion to the topcoat mixture at a low speed over 2 minutes. Then dilute the coating with water to the appropriate flow cup viscosity.

[0236] Table 3: Topcoat Coating Compositions Containing PTFE

[0237]

[0238] Table 4: PTFE-free topcoat coating compositions

[0239]

[0240] *CYMEL 303LF is a methylated melamine crosslinking agent, available from Zhanxin.

[0241] BYK-333 is a polyester-modified polydimethylsiloxane available from Byk (Altana Group). NACURE 155 (hydrophobic sulfonic acid catalyst) and NACURE 3525 (amine-neutralized dinonylnaphthalene disulfonic acid catalyst) are available from King Industries. MAGIESOL 52 (hydrotreated petroleum fraction) is available from Calome.

[0242] Preparation of coated can

[0243] Use a Wagner can coater to apply the clear coat to the appropriate substrate.

[0244] 1. For topcoat application, use 1.5 to 2.5 layers of coating to coat the straight-walled, two-piece aluminum can.

[0245] 2. Then cure the topcoat in a box oven at 400℉ for 1 minute.

[0246] 3. Then apply the internal spray coating to the inside of the can and cure to achieve a peak metal temperature (PMT) of over 380℉ for more than 60 seconds, or a peak metal temperature (PMT) of over 400℉ for 3 seconds.

[0247] 4. Use an 18-level pilot necking machine to neck the can.

[0248] Test Results

[0249] AGR / CQF (Coefficient of Friction) of the Tilted Table Filling Tank

[0250] The topcoat layer was tested according to the above test method. The results are shown in Table 4.

[0251] The topcoat layer of this disclosure may have an AGR / tilted table filled tank COF of 9°, 10°, 11° to 12°, 13°, 14° or any range such as 9° to 14°, 10° to 13° or 11° to 12° using any of the foregoing values ​​as endpoints.

[0252] Altek directly CQF

[0253] The topcoat layer was tested according to the above test method. The results are shown in Table 4.

[0254] The topcoat layer of this disclosure may have an Altek direct COF of 0.030, 0.050, 0.070 to 0.080, 0.090, 0.100, or any range including any of the aforementioned values ​​as endpoints, such as 0.030 to 0.100, 0.050 to 0.090, or 0.070 to 0.080.

[0255] Altek Face-to-Face CQF

[0256] The topcoat layer was tested according to the above test method. The results are shown in Table 4.

[0257] The topcoat layer of this disclosure may have an Altek face-to-face COF of 0.060, 0.080, 0.100 to 0.120, 0.140, 0.150, or any range including any of the aforementioned values ​​as endpoints, such as 0.060 to 0.150, 0.080 to 0.140, or 0.100 to 0.120.

[0258] MEK dual friction

[0259] The topcoat layer was tested according to the above test method. The results are shown in Table 4.

[0260] The topcoat layer disclosed herein may have a MEK dual friction value greater than 20, greater than 40, greater than 60, greater than 80, or greater than 100.

[0261] Pencil hardness

[0262] The topcoat layer was tested according to the above test method. The results are shown in Table 4.

[0263] The varnish layer disclosed herein can have a pencil hardness of 2B to 6H.

[0264] TQCAT: Test Methodology

[0265] The topcoat layer was tested according to the above test method. The results are shown in Table 5.

[0266] Table 4: Cured Film Test

[0267]

[0268] Table 5: TQCAT Results

[0269]

[0270] *MSI = milligrams per square inch** AS = wear fraction

[0271] Example 2:

[0272] Tactile Topcoat

[0273] 1. Comparison Examples:

[0274] The wax currently used is a blend of 0.86% polyethylene and 1.3% PTFE based on resin solids. Other additives include 0.12% Coatosil 7605, a silicone-polyether block copolymer. The polyether type is EO.

[0275] 2. Examples of Inventions:

[0276] The wax used in the commercially available, fluoropolymer-free product is 1.92% RS Fischer-Tropsch (FT) wax from Sasol. Other additives are 0.10% RS Coatosil 7605 (as described above) and 0.24% RS HiSil T-800. HiSil T-800 is a precipitated silica product from PPG.

[0277] Comparative Example 1 and Invention Example 1 were prepared according to Table 6.

[0278] Table 6: Preparation of Comparative Example 1 and Invention Example 1

[0279]

[0280] The test results using the tribometer test method for the coating layer of Comparative Example 1 and Invention Example 1 are shown in Table 7.

[0281] Table 7: Test Results of Comparative Example 1 and Invention Example 1

[0282]

[0283] Example: 3

[0284] Glossy Topcoat

[0285] 1. Comparison Examples:

[0286] The wax currently used is a blend of 0.62% RS PE and 0.95% RS PTFE. Other additives include 0.33% RS PDMS.

[0287] 2. Examples of Inventions:

[0288] The wax used in commercial products that do not contain fluoropolymers is 1.76% RS Fischer-Tropsch (FT) wax from Sasol. Other waxes and wax blends are PE and bio-based waxes. All examples are included in the table below.

[0289] Compare Examples 2 to 7, prepared according to Table 8.

[0290] Table 8: Comparative Examples 2 to 7 Formulas

[0291]

[0292] Invention Examples 2 to 10 are prepared according to Table 9.

[0293] Table 9: Formulations of Invention Examples 1 to 9

[0294]

[0295] The test results of the topcoat layers in comparative examples 1 to 6 and inventive examples 1 to 9 are shown in Table 10 and Figure 1 As shown.

[0296] Table 10: Test results of comparative examples 2 to 7 and inventive examples 2 to 10

[0297]

[0298] Specific examples of the invention have been described above for illustrative purposes, and it will be apparent to those skilled in the art that many detailed changes can be made to the invention without departing from the invention as defined in the appended claims. Therefore, this application is intended to cover any variations, uses, or adaptations of this disclosure using its general principles. Furthermore, this application is intended to cover any deviations from this disclosure within the scope of known or conventional practice in the art to which this disclosure pertains, and which fall within the limitations of the appended claims.

Claims

1. A topcoat composition comprising: Film-forming resin; Crosslinked materials; Lubricant; The lubricant is at least one of polyethylene wax, Fischer-Tropsch wax, and bio-wax; and At least one additive; The aforementioned topcoat composition is substantially free of perfluorinated and polyfluorinated substances.

2. The coating composition according to claim 1, further comprising precipitated silica.

3. The coating composition according to claim 1 or claim 2, further comprising an organosilicon copolymer.

4. The coating composition according to any one of claims 1 to 3, wherein the film-forming resin comprises at least one selected from polyester, acrylic polymer, polyurethane resin and epoxy resin.

5. The coating composition according to any one of claims 1 to 4, wherein the lubricant comprises microcrystalline polyethylene.

6. The coating composition according to any one of claims 1 to 5, wherein the lubricant is present in an amount of 0.1 wt.% to 3 wt.% based on the total weight of the coating composition.

7. The coating composition according to any one of claims 1 to 6, wherein the at least one additive is at least one selected from slip agent, tackifier, plasticizer, surfactant, flow control agent, defoamer, thixotropic agent, filler, diluent, organic solvent, matting agent and catalyst.

8. The coating composition according to any one of claims 1 to 7, wherein the at least one additive comprises a slip agent.

9. The coating composition according to any one of claims 1 to 8, wherein the crosslinking material is present in an amount of 10 wt.% to 35 wt.% based on the total weight of the coating composition.

10. The coating composition according to any one of claims 1 to 9, wherein the coating composition is a thermosetting composition.

11. A package having at least a portion of its outer surface coated with a topcoat derived from a coating composition according to any one of claims 1 to 10.

12. The packaging according to claim 11, wherein the packaging comprises a metal can.

13. The packaging according to claim 11 or claim 12, wherein the packaging includes food and / or beverage packaging.

14. The packaging according to any one of claims 11 to 13, wherein the varnish is applied over at least a portion of the ink coating and / or the base coating.

15. The packaging according to any one of claims 11 to 14, wherein the thickness of the topcoat layer is at least 2 µm.

16. The packaging according to any one of claims 11 to 15, wherein the topcoat has a coefficient of friction of 0.057 to 0.15 according to a tribometer test method.

17. The packaging according to any one of claims 11 to 16, wherein the topcoat layer has 2,000 to 6,800 failure cycles according to the tribometer test method.

18. The packaging according to any one of claims 11 to 17, wherein the lubricant has a melting point of 80°C to 115°C as measured by differential scanning calorimetry (DSC).

19. A method for coating food and / or beverage packaging, comprising: At least a portion of the outer surface of the food and / or beverage packaging is coated with a topcoat composition comprising a film-forming resin, a crosslinking material, a lubricant, and at least one additive. The lubricant described herein comprises at least one of polyethylene wax, Fischer-Tropsch wax, and bio-wax; and The coating composition is substantially free of perfluorinated and polyfluorinated substances (PFAS).

20. The method of claim 19, further comprising curing the topcoat composition at a peak metal temperature of 170°C to 230°C.

21. A method for coating food and / or beverage packaging, comprising: The outer surface of the food and / or beverage packaging is coated with a topcoat composition comprising a film-forming resin, a crosslinking material, a lubricant, a silicone-modified polymer, precipitated silica, and at least one additive. The lubricant mentioned above contains Fischer-Tropsch wax; The coating composition is substantially free of perfluorinated and polyfluorinated substances (PFAS).

22. The method of claim 21, further comprising curing the topcoat composition at a peak metal temperature of 170°C to 230°C.

Images