Use of coating composition and method of coating cans

Abstract

Use of a coating composition for reducing or preventing insufficient venting of a beverage can comprising a can body and a can end having a score line on the can end wherein the coating composition comprises a polyester material wherein the coating composition is applied to at least an inner surface of the can end over at least a portion of the score line, and wherein a cured film formed from the coating composition has a glass transition temperature (Tg) of at least 50 DEG C. A method of coating a can comprising a can body and an end of the can having a score line on the end of the can wherein the method comprises applying a coating composition to at least a portion of an inner surface of the end of the can over at least a portion of the score line, the coating composition comprising a polyester material; and curing the coating composition to form a cured film wherein the cured film has a glass transition temperature (Tg) of at least 50 DEG C wherein the can, when filled with a carbonated beverage and sealed, exhibits sufficient venting upon rupture of the score line.

Description

[0001] This application is a divisional application of Chinese patent application No. 201880064434.4, filed on August 31, 2018, entitled “Use of coating composition and method of coating can”. Technical Field

[0002] This invention relates to the use of coating compositions and methods of coating cans. In particular, this invention relates to the use of coating compositions comprising polyester materials for reducing or preventing insufficient venting from beverage cans and to methods relating to coating beverage cans containing carbonated beverages to reduce or prevent insufficient venting from the beverage cans. Background Technology

[0003] Beverage cans are known in the art and typically include a can body and at least one can end. For example, a beverage can may be a two-piece can comprising a can body having an integral bottom portion and a can end attached thereto, or a beverage can may be a three-piece can comprising a can body, such as a substantially cylindrical can, and top and bottom can ends attached thereto. The can end may have a notch defining a portion of the can end to be opened, such that, upon opening, the contents of the can can be removed, for example, by pouring. The notch facilitates shearing around the outer periphery of the portion of the can end to be opened, and thus facilitates removal of the portion of the can end to be opened.

[0004] In the case of beverage cans containing carbonated beverages, such as beer or soda, sufficient carbon dioxide should be allowed to escape from the can substantially immediately upon opening, thus preventing the gas from accumulating inside. Opening a carbonated beverage can breaks the mechanical seal of the portion of the can to be opened, i.e., causes the metal to crack along the score line. However, the coating seal, i.e., the paint composition covering the score line, should also be broken simultaneously; otherwise, the coating composition could continue to cover the gap created when the mechanical seal is broken (causing the score line), thereby preventing carbon dioxide from escaping from the beverage can. Releasing carbon dioxide from the beverage can upon opening is called "venting." If insufficient venting occurs, i.e., if an insufficient amount of carbon dioxide is released substantially immediately upon opening the beverage can, pressure can accumulate inside the beverage can because the coating seal is not broken, potentially leading to the coating seal eventually rupturing under pressure and the beverage can exploding. Therefore, sufficient venting should be demonstrated when the score line is broken.

[0005] Therefore, it is desirable to provide a coating composition for use in the opening of a beverage can that can reduce or prevent insufficient venting of the beverage by breaking cleanly when the score line breaks. Summary of the Invention

[0006] The present invention relates to the use of a coating composition in reducing or preventing insufficient venting in a beverage can comprising a can body and a can end having a score line on the can end, wherein the coating composition comprises a polyester material, wherein the coating composition is applied to at least an inner surface of the can end on at least a portion of the score line, and wherein a cured film formed by the coating composition has a glass transition temperature (Tg) of at least 50°C.

[0007] This invention relates to a method of coating a can comprising a can body and a can end having score lines on the can end, wherein the method comprises applying a coating composition comprising a polyester material to at least a portion of an inner surface of the can end along at least a portion of the score lines; and curing the coating composition to form a cured film, wherein the cured film has a glass transition temperature (Tg) of at least 50°C.

[0008] The can, when filled with carbonated beverage and sealed, exhibits sufficient venting when the scoring line breaks. Detailed Implementation

[0009] The present invention relates to the use of a coating composition in reducing or preventing insufficient venting in a beverage can comprising a can body and a can end having a score line on the can end, wherein the coating composition comprises a polyester material, wherein the coating composition is applied to at least an inner surface of the can end on at least a portion of the score line, and wherein a cured film formed by the coating composition has a glass transition temperature (Tg) of at least 50°C.

[0010] The present invention relates to a method of coating a can comprising a can body and a can end having a score line on the can end, wherein the method comprises applying a coating composition on at least a portion of the score line to at least a portion of an inner surface of the can end, the coating composition comprising a polyester material;

[0011] And to cure the coating composition to form a cured film, wherein the cured film has a glass transition temperature (Tg) of at least 50°C.

[0012] The can, when filled with carbonated beverage and sealed, exhibits sufficient venting when the scoring line breaks.

[0013] As used herein, “sufficient venting” and similar terms, unless otherwise stated, mean that a sufficient amount of gas, such as carbon dioxide, is released substantially immediately upon breaking the score line to ensure that pressure does not build up inside the beverage can. Suitably, sufficient gas, such as carbon dioxide, is released substantially immediately upon breaking the score line so that the pressure on the inside of the beverage can is substantially equal to the pressure on the outside of the beverage can. The degree of venting can be measured according to the overturning test as described in the Examples section. Overturning occurs at the point where the score line breaks, but the internal pressure of the can is not released immediately due to carbonation, causing the opening of the can to break open and protrude from the can, rather than enter the can (or be inverted), as is typical when opening a can. “Insufficient venting” will be understood as the opposite of what has been described above.

[0014] The can end of the present invention has a scoring line thereon. A “scoring line” means a line that partially cuts into the can end, such that the line does not extend all the way through the can end, and the scoring line defines a portion of the can end to be opened (the opening portion). Suitably, the scoring line is deep and wide enough that it facilitates breaking around the periphery of the opening portion when a thrust and / or pull force is applied to the portion of the can end to be opened. Such scoring lines are well known to those skilled in the art.

[0015] To avoid ambiguity, the term "break the score line" means damaging the score line at the end of the can, thereby shearing the mechanical seal. A mechanical seal is a seal formed by a metal substrate forming the end of a beverage can, such as a seal formed by a can end having score lines thereon. In contrast, a coating seal is a seal formed by a cured film derived from one or more coating compositions applied to at least a portion of the score line onto the inner surface of the can end. The score line can be broken by applying a tensile and / or thrust force to the portion of the can end to be opened.

[0016] Polyester materials include copolymers of polyacids and polyols, and also include modified polyesters, such as polyesters modified by grafting additional polymers onto the polyester. Examples of modified polyesters include acrylic-modified polyester resins.

[0017] Polyester materials can include any suitable polyester material. Polyester materials can include reaction products comprising a reaction mixture of a polyacid and a polyol. Polyester materials can be obtained by polymerizing a polyacid and a polyol.

[0018] 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 esters (where one or more acid groups are esterified) or anhydrides of polyacids. Polyacids are suitably organic polyacids.

[0019] The carboxylic acid groups of polyacids in polyester materials can be connected by bridging groups selected from the following: alkylene groups; alkenylene groups; ynylene groups; or arylene groups.

[0020] Polyester materials can be formed from any suitable polybasic acid. Suitable examples of polybasic acids include, but are not limited to, the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; selenic acid; glutaric acid; sebacic acid; dodecanoic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalenedicarboxylic acid; naphthalenetetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexanedicarboxylic acid; chlorobridged anhydride; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; tricyclodecane polycarboxylic acid; inner methylenetetrahydrophthalic acid; inner ethylhexahydrophthalic acid; cyclohexanetetracarboxylic acid; cyclobutanetetracarboxylic acid; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the aforementioned acids, and combinations thereof.

[0021] Suitablely, the carboxylic acid group of a polybasic acid may be linked by an arylene bridging group. Therefore, suitablely, polybasic acids may include aromatic polybasic acids.

[0022] The polybasic acid component may include terephthalic acid (TPA), isophthalic acid (IPA), dimethyl terephthalate, dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalenedicarboxylic acid, adipic acid, phthalic anhydride, maleic anhydride and / or fumaric anhydride.

[0023] Polyester materials can be formed from diacids. Suitable examples of diacids include, but are not limited to, the following: phthalic acid; isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebaceous acid; fumaric acid; 2,6-naphthalenedicarboxylic acid; phthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; diester materials, such as dimethyl ester derivatives, such as dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, dimethyl fumarate, dimethyl phthalate, dimethyl succinate, dimethyl glutarate, dimethyl adipate; monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the aforementioned acids; and mixtures thereof.

[0024] 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 may be linked by bridging groups selected from: alkylene groups; alkenylene groups; ynylene groups; or arylene groups. Suitably, the polyol is an organic polyol.

[0025] Polyester materials can be formed from any suitable polyol. Suitable examples of polyols include, but are not limited to, the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycols, including 1,2-propanediol; 1,3-propanediol; butyl ethyl propylene glycol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; butanediols, including 1,4-butanediol; 1,3-butanediol; 2,2,4,4-tetraalkyl-1,3-cyclobutanediol, such as 2,2,4,4-tetramethyl -1,3-cyclobutanediol; and 2-ethyl-1,4-butanediol; pentanediols, including trimethylpentanediol and 2-methylpentanediol; cyclohexanediol; hexanediols, including 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; biogenic polyols such as glycerol, sorbitol; and / or monomers having an aliphatic group containing at least 15 carbon atoms, or combinations thereof.

[0026] Suitablely, polyols may include cyclohexanediol, 2-methyl-1,3-propanediol, ethylene glycol, and combinations thereof.

[0027] Polyester materials can be formed from diols. Suitable examples of 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-en-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; 2,2,4,4-Tetramethylcyclobutane-1,3-diol; Isosorbide; 1,4-Cyclohexanediol; 1,1'-Isopropylidene-bis(4-cyclohexanol); and mixtures thereof.

[0028] The polyol component may include polyols having at least three hydroxyl groups, such as trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; and / or bio-derived polyols, such as glycerol and / or sorbitol. Suitably, the polyol component having at least three hydroxyl groups includes triols and / or tetraols, such as trimethylolpropane; pentaerythritol; trimethylolethane; trimethylolbutane; and / or glycerol. Suitably, the polyol component having at least three hydroxyl groups may include triols, such as trimethylolpropane; trimethylolethane; and / or trimethylolbutane, for example, trimethylolpropane.

[0029] Polyols having at least three hydroxyl groups may be present in amounts of 0.1 to 10 wt%, such as 0.5 to 8 wt% or 0.7 to 6 wt%, such as 0.8 to 5 wt% or 0.9 to 4 wt%, suitably 1 to 3 wt% or 1 to 2 wt%, based on the dry weight of the polyol component.

[0030] The polyol component may include: 2-methyl-propanediol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexanediol (CHDM), butyl ethyl propylene glycol (BEPD), trimethylolpropane (TMP), and / or 1,6-hexanediol.

[0031] Polyester materials containing polyacid components and / or polyol components or acrylic polyester resins may contain monomers that enhance Tg, including:

[0032] (i) A polyacid or polyol containing an optionally substituted naphthalene group, or a hydrogenated derivative thereof;

[0033] (ii) A polyacid or polyol comprising two optionally substituted 5- or 6-membered cyclic groups, wherein the cyclic groups do not share atoms, and wherein the cyclic groups are directly bonded or separated by a carbon atom.

[0034] (iii) A polyacid or polyol containing an optionally substituted furan group;

[0035] (iv) A polyacid or polyol containing optionally substituted fused bicyclic groups, wherein each ring is a five-membered ring and one or two of the rings may contain heteroatoms in the ring;

[0036] (v) Polyacids or polyols containing optionally substituted bridged tricyclic decyl groups;

[0037] (vi) A polyacid or polyol containing an optionally substituted bridged norbornene group, or a hydrogenated derivative thereof;

[0038] (vii) Polyacids or polyols containing optionally substituted 5- or 6-membered cycloalkyl or aromatic groups;

[0039] (viii) A polyacid or polyol monomer containing a branched alkyl group, wherein the monomer contains at least one quaternary carbon atom and is formed of 5 to 10 carbon atoms, and wherein the carbon atom bonded to the acid or hydroxyl group is a primary carbon atom.

[0040] (ix) a polyacid or polyol containing an optionally substituted tetraoxaspiro[5.5]undecyl group; and / or

[0041] (x) Diol according to formula (I)

[0042]

[0043] R1 and R2 each independently represent a hydrogen group, a lower alkyl group, or an aryl group having 6 to 12 carbon atoms, wherein at least one of R1 or R2 is a lower alkyl group or an aryl group having 6 to 12 carbon atoms; and R3 and R4 each independently represent a lower alkyl group or an aryl group having 6 to 12 carbon atoms.

[0044] Monomers that increase Tg refer to monomers that increase the Tg of polyester resins and / or cured films formed from coating compositions, compared to the same polyester resin or cured film composition except for those that do not contain the monomers that increase Tg.

[0045] Monomers that increase Tg may include monomer (i). Hydrogenated derivatives of monomer (i) that increase Tg may be fully or partially hydrogenated. Therefore, hydrogenated derivatives of (i) may be unsaturated. Suitably, hydrogenated derivatives of (i) are saturated. Monomers (i) that increase Tg may include 2,6-naphthalenedicarboxylic acid, 1,8-dihydroxynaphthalene and / or hydrogenated 1,8-dihydroxynaphthalene, and / or esters and / or anhydrides of all the aforementioned acids.

[0046] Monomers that improve Tg may include monomer (ii). The cyclic group of monomer (ii) that improves Tg may be aromatic or alicyclic. Monomer (ii) may contain two optionally substituted 6-membered cyclic groups. Suitably, monomer (ii) may contain two directly bonded optionally substituted 6-membered aromatic cyclic groups. Suitably, monomer (ii) may contain two optionally substituted 6-membered alicyclic cyclic groups separated by a carbon atom, and suitably, the alicyclic group of monomer (ii) is cycloalkyl. "Directly bonded" as used herein means that a ring atom in one of the two cyclic groups is covalently bonded to a ring atom in the other cyclic group. Monomer (ii) that improves Tg may include hydrogenated bisphenol A and / or esters and / or anhydrides of 2-(2-carboxyphenyl)benzoic acid and / or all of the aforementioned acids.

[0047] Monomers that increase Tg can include monomer (iii). Monomers that increase Tg (iii) can include esters and anhydrides of 2,5-furandicarboxylic acid and all of the aforementioned acids.

[0048] Monomers that increase Tg can include monomer (iv). Monomer (iv) can include heteroatoms in the ring, preferably one heteroatom in each ring, and preferably the heteroatom is an oxygen or nitrogen atom, such as an oxygen atom. Monomers (iv) that increase Tg can include isosorbide and / or isomannitol.

[0049] Monomers that improve Tg may include monomer (v). The optionally substituted bridged tricyclic decyl group of monomer (v) may be saturated or unsaturated, suitably saturated. The optionally substituted bridged tricyclic decyl group may be tricyclic [5.2.1.0(2,6)]decane. Monomers (v) that improve Tg may include tricyclic decanediethanol, tricyclic decanediol, and / or tricyclic decane polycarboxylic acids and / or esters and / or anhydrides of all the aforementioned acids.

[0050] Monomers that increase Tg may include monomer (vi). Optionally substituted hydrogenated derivatives of monomer (vi) with bridged norbornene groups may include optionally substituted norbornene. Monomers (vi) that increase Tg may include nadic methyl acid, nadic acid, and / or chlorobridged anhydride and / or esters and / or anhydrides / acids of all the aforementioned acids / anhydrides.

[0051] Monomers that improve Tg may include monomer (vii). The optionally substituted 5- or 6-membered cycloalkyl groups of monomer (vii) may be saturated or partially unsaturated. Monomers that improve Tg (vii) may include cyclohexanediethanol, cyclohexanediol, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylate, isophthalic acid, phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; inner methylene tetrahydrophthalic acid; inner ethylhexahydrophthalic acid; phthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; dimethyl phthalate and / or terephthalic acid and / or esters and / or anhydrides of all the aforementioned acids.

[0052] Monomers that increase Tg can include monomer (viii). Monomers containing branched alkyl groups (viii) can be formed from 5 to 8 carbon atoms, such as 5 to 7 carbon atoms, 5 to 6 carbon atoms, or 5 carbon atoms. Monomers that increase Tg (viii) can include neopentyl glycol.

[0053] Monomers that improve Tg may include monomer (ix). Monomer (ix) may be 3,9-bis(1,1-dialkyl-2-hydroxyethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane, wherein the alkyl group is methyl, ethyl, or propyl. Suitably, monomer (ix) includes 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane.

[0054] Monomers that increase Tg may include monomer (x). The R1 and R2 groups of the diol according to formula (I) may each independently represent hydrogen, a lower alkyl group, or an aryl group having 6 to 12 carbon atoms, wherein at least one of R1 or R2 is a lower alkyl group. The R3 and R4 groups of the diol according to formula (I) may each independently represent a lower alkyl group or an aryl group having 6 to 12 carbon atoms, wherein at least one of R3 or R4 is a lower alkyl group.

[0055] The aryl group of the diol according to formula (I) may have 6 to 10 carbon atoms, such as 6 to 8 carbon atoms or 6 carbon atoms. The R1 and R2 groups of the diol according to formula (I) may each independently represent hydrogen or a lower alkyl group, wherein at least one of R1 or R2 is a lower alkyl group. The R3 and R4 groups of the diol according to formula (I) may each independently represent a lower alkyl group.

[0056] The R1, R2, R3, and R5 groups of the diol according to formula (I) can each independently represent a lower alkyl group. The lower alkyl group can be an alkyl group having 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 a straight-chain, branched, or a combination of straight-chain and branched alkyl groups. The diol according to formula (I) can include 2,2,4-trimethyl-1,3-pentanediol (TMPD).

[0057] Monomers that increase Tg can include 2,6-naphthalenedicarboxylic acid, 1,8-dihydroxynaphthalene, hydrogenated 1,8-dihydroxynaphthalene, hydrogenated bisphenol A, 2-(2-carboxyphenyl)-benzoic acid, 2,5-furandicarboxylic acid, isosorbide, isomannitol, tricyclodecanediethanol, tricyclodecanediol, tricyclodecanepolycarboxylic acid, nadic acid, nadic methyl acid, nadic acid, chlorobridged anhydride, cyclohexanediethanol, cyclohexanediol, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylate, neopentyl glycol, 3,9-bis(1,1-dimethyl) -2-hydroxyethyl)-2,4,8,10-tetraoxaziro[5.5]undecane, isophthalic acid, phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; inner methylene tetrahydrophthalic acid; inner ethylhexahydrophthalic acid; phthalic acid; phthalic anhydride; 2,2,4-trimethyl-1,3-pentanediol, tetrahydrophthalic anhydride; dimethyl phthalate and / or terephthalic acid and / or esters and / or anhydrides / acids of all the foregoing acids / anhydrides.

[0058] The amount of Tg-enhancing monomers in the polyol and polyacid components can be the amount required to impart a desired Tg in the polyester material and / or a cured film formed from a coating composition containing polyester material. For example, the amount of Tg-enhancing monomers (i) to (x) in the polyol and / or polyacid components can be the amount required to achieve a Tg of at least 50°C, or at least 55°C, or at least 60°C, such as at least 65°C or at least 70°C, in the polyester material and / or a cured film formed from a coating composition containing polyester material.

[0059] If used, the monomers (i) to (x) that increase Tg may be present in an amount of 10 mol%, based on the total mol% of the combined polyacid and polyol components. Suitably, if used, the monomers that increase Tg may account for at least 20 mol%, such as at least 30 mol%, at least 40 mol%, or at least 50 mol%, based on the total mol% of the combined polyacid and polyol components.

[0060] The cured film formed from the coating composition has a glass transition temperature (Tg) of at least 50°C.

[0061] The cured film formed from the coating composition can have a glass transition temperature (Tg) of at least 55°C.

[0062] The cured film formed from the coating composition can have a glass transition temperature (Tg) of at least 60°C.

[0063] The cured film formed from the coating composition may have a glass transition temperature (Tg) of at least 65°C, such as at least 70°C.

[0064] The cured film formed from the coating composition can have a glass transition temperature (Tg) of up to 200°C.

[0065] The cured film formed from the coating composition can have a glass transition temperature (Tg) of up to 150°C.

[0066] The cured film formed from the coating composition can have a glass transition temperature (Tg) of up to 120°C.

[0067] The cured film formed from the coating composition can have a glass transition temperature (Tg) of up to 110°C.

[0068] The cured film formed from the coating composition can have a glass transition temperature (Tg) of up to 105°C.

[0069] The cured film formed from the coating composition can have a glass transition temperature (Tg) of 50 to 200°C, suitably 50 to 150°C, such as 50 to 120°C, such as 50 to 110°C, or even 50 to 105°C. The cured film formed from the coating composition can have a glass transition temperature (Tg) of 60 to 200°C, suitably 60 to 150°C, such as 60 to 120°C, such as 60 to 110°C, or even 60 to 105°C. The cured film formed from the coating composition can have a glass transition temperature (Tg) of 70 to 200°C, suitably 70 to 150°C, such as 70 to 120°C, such as 70 to 110°C, or even 70 to 105°C. The cured film formed from the coating composition can have a glass transition temperature (Tg) of 75 to 200°C, suitably 75 to 150°C, such as 75 to 120°C, such as 75 to 110°C, or even 75 to 105°C.

[0070] Suitablely, the cured film formed from the coating composition can have a glass transition temperature (Tg) of 65 to 110°C.

[0071] Polyester materials may have a Tg of at least 50°C, such as at least 55°C or at least 60°C. Polyester materials may have a Tg of at least 65°C or at least 70°C. Polyester materials may have a Tg of up to 120°C, such as up to 115°C, such as up to 110°C, such as up to 105°C. Polyester materials may have a Tg of up to 100°C.

[0072] Polyester materials can have a Tg of 50°C to 120°C, such as 60°C to 105°C.

[0073] The Tg mentioned in this document is measured as defined in the Test Methods section below.

[0074] At least one of the polyacid and / or polyol components of the polyester material may include a monomer having an aliphatic group containing at least 15 carbon atoms.

[0075] Further details of such monomers having aliphatic groups containing at least 15 carbon atoms are disclosed in published PCT patent application WO 2018 / 111854, specifically paragraphs

[016] to

[030] . The entire contents of WO 2018 / 111854, and especially paragraphs

[016] to

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

[0076] Suitably, the polyacid component and / or polyol component may include sulfonated monomers. Sulfonated monomers may include sulfonated diacids, such as sulfonated aromatic diacids. Sulfonated monomers may include their salts, such as inorganic salts, for example, metal or ammonium salts. Examples of metal salts would include, for example, sodium salts, lithium salts, potassium salts, magnesium salts, calcium salts, iron salts, etc.

[0077] Suitablely, the polybasic acid component may include sulfonated monomers. Alternatively, the polybasic acid component may be substantially free of sulfonated monomers.

[0078] Suitablely, 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 oxysulfonyl)-isophthalic acid, and is also referred to herein as 5-SSIPA.

[0079] Suitably, the sulfonated monomer may include: 5-(sodium oxysulfonyl)-isophthalic acid, dimethyl 5-(sodium oxysulfonyl)isophthalate, 5-(lithiosulfo))isophthalic acid and / or bis(2-hydroxyethyl)-5-(sodium oxysulfonyl)isophthalate.

[0080] When the sulfonated monomer is a polybasic acid, the sulfonated monomer may be present in an amount of 5 to 20 wt%, such as 7 to 15 wt%, based on the dry weight of the polybasic acid component.

[0081] When the sulfonated monomer is a polyol, the sulfonated monomer may be present in an amount of 5 to 20 wt%, such as 7 to 15 wt%, based on the dry weight of the polyol component.

[0082] Polyester materials can optionally be formed from other monomers.

[0083] Other monomers may include monocarboxylic acids. As used herein, "monocarboxylic acid" and similar terms refer to compounds having a carboxylic acid group and comprising esters (wherein the acid group is esterified) or anhydrides of a monocarboxylic acid. Monocarboxylic acids are suitably organic monocarboxylic acids.

[0084] Suitable examples of monocarboxylic acids include, but are not limited to, the following: 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 aforementioned acids and combinations thereof.

[0085] Other monomers may include monohydric alcohols. As used herein, “monohydric alcohol” and similar terms refer to compounds having a hydroxyl group. Suitably, monohydric alcohols are organic monohydric alcohols.

[0086] Suitable examples of monohydric alcohols include, but are not limited to, the following: benzyl alcohol; hydroxyethoxybenzene; methanol; ethanol; propanol; butanol; pentanol; hexanol; heptanol; dodecyl alcohol; stearyl alcohol; oleyl alcohol; undecyl alcohol; cyclohexanol; phenol; benzyl alcohol; methylbenzyl alcohol; cresol; monoethers of diols; halogenated or otherwise substituted alcohols and combinations thereof.

[0087] In this article, "aliphatic" includes alicyclic groups, which are saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridged, and spirofused) ring systems having 3 to 20 carbon atoms, i.e., alicyclic groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Alicyclic groups can contain 3 to 15, such as 3 to 12, or 3 to 10, or 3 to 8 carbon atoms, such as 3 to 6 carbon atoms.

[0088] The term "alicyclic" includes cycloalkyl, cycloalkenyl, and cycloynyl groups. It will be appreciated that alicyclic groups can include alicyclic rings with linked or unlinked alkyl substituents, such as –CH2-cyclohexyl. In particular, C… 3-20 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantly, isobornyl, and cyclooctyl.

[0089] Unless otherwise specified, the terms "alkane" or "alkyl" as used herein refer to a saturated hydrocarbon group that is a straight-chain, branched, cyclic, or polycyclic moiety or a combination thereof and contains 1 to 20 carbon atoms, suitably 1 to 10 carbon atoms, more suitably 1 to 8 carbon atoms, even more suitably 1 to 6 carbon atoms, and still more suitably 1 to 4 carbon atoms. These groups may optionally be substituted with chlorine, bromine, iodine, cyano, nitro, or... 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 aryl or heteroatom, wherein R 19 To R 27 Each group independently represents hydrogen, aryl, or alkyl and / or is interrupted by an oxygen or sulfur atom, or by a silano or dialkylsiloxane group. Examples of such groups can be independently selected from 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 by –CH3, becomes methylene –CH2- when represented as alkylene. Other alkylene groups should be understood accordingly.

[0090] As used herein, the term "alkenyl" refers to a hydrocarbon group having double bonds, preferably up to four double bonds, which is a straight-chain, branched, cyclic, or polycyclic structural moiety or a combination thereof and contains 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. These groups may optionally be substituted with: hydroxyl, chlorine, bromine, iodine, cyano, nitro, OR 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, where R19 To R 27 Each group independently represents hydrogen, aryl, or alkyl and / or is interrupted by an oxygen or sulfur atom, or by a silanol or dialkylsiloxane group. Examples of such groups can be independently selected from alkenyl groups including vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, isopentenyl, 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 which would be represented by –CH=CH2, becomes vinylene-CH=CH- when represented as an alkenyl group. Other alkenyl groups should be understood accordingly.

[0091] As used herein, the term "alkynyl" refers to a hydrocarbon group having three bonds, preferably up to four, which is a straight-chain, branched, cyclic, or polycyclic structural moiety or a combination thereof and has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. These groups may optionally be substituted with hydroxyl, chlorine, bromine, iodine, cyano, nitro, or OR. 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, where R 19 To R 27 Each group independently represents hydrogen, an aryl or lower alkyl group and / or is interrupted by an oxygen or sulfur atom, or by a silanol or dialkylsiloxane group. Examples of such groups can be independently selected from alkynyl groups, including ethynyl, propynyl, propynyl, butynyl, pentyynyl, hexynyl, etc. As used herein, the term "ynynyl" refers to a divalent alkynyl group as defined above. For example, an alkynyl group, such as a vinyl group which would be represented by –C≡CH, becomes ethynyl-C≡C- when represented as ynynyl. Other ynynyl groups should be understood accordingly.

[0092] As used herein, the term "aryl" refers to an organic group derived from an aromatic hydrocarbon by removing a hydrogen atom and comprising any monocyclic, bicyclic, or polycyclic carbon ring, each ring having up to 7 members, wherein at least one ring is aromatic. These groups may optionally be substituted with: hydroxyl, chlorine, bromine, iodine, cyano, nitro, or...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, where R 19 To R 27 Each of these groups independently represents hydrogen, aryl or lower alkyl and / or is interrupted by an oxygen or sulfur atom, or by a silanol or dialkylsilane group. Examples of such groups can be independently selected from 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 a divalent aryl group as defined above. For example, aryl groups, such as phenyl groups which would be represented by –Ph, become phenylene –Ph- when represented as arylene. Other arylene groups should be understood accordingly.

[0093] To avoid ambiguity, references to alkyl, alkenyl, alkynyl, aryl, or aralkyl groups in this document, such as "alkyl" in aminoalkyl or "alkane" in alkoxy, should be interpreted as "alkane" or "alkyl" as described above.

[0094] Polyester materials can have any suitable number-average molecular weight (Mn).

[0095] Polyester materials may have a Mn content of at least 500 Daltons (Da = g / molar).

[0096] Polyester materials can have Mn of at least 1000 Da.

[0097] Polyester materials can have Mn of at least 2,000 Da.

[0098] Polyester materials can have Mn of at least 3,000 Da.

[0099] Polyester materials can have a Mn content of at least 4,000 Da.

[0100] Polyester materials can have a Mn content of at least 5,000 Da.

[0101] Polyester materials can have a Mn content of at least 6,000 Da.

[0102] Polyester materials can have a Mn content of at least 7,000 Da.

[0103] Polyester materials can have a Mn content of at least 8,000 Da.

[0104] Polyester materials can have a Mn content of at least 9,000 Da.

[0105] Polyester materials can have a Mn content of at least 10,000 Da.

[0106] Polyester materials can have a Mn content of at least 15,000 Da.

[0107] Polyester materials can have a maximum Mn content of 250,000 Da.

[0108] Polyester materials can have a maximum Mn content of 200,000 Da.

[0109] Polyester materials can have a maximum Mn content of 150,000 Da.

[0110] Polyester materials can have a maximum Mn content of 100,000 Da.

[0111] Polyester materials can have a maximum Mn content of 50,000 Da.

[0112] Polyester materials can have a maximum Mn content of 25,000 Da.

[0113] Polyester materials can have Mn ranging from 500 to 250,000 Da, preferably from 500 to 200,000 Da, such as 500 to 150,000 Da, such as 500 to 100,000 Da, such as 500 to 50,000 Da, or even 500 to 25,000 Da. Polyester materials can also have Mn ranging from 1,000 to 250,000 Da, preferably from 1,000 to 200,000 Da, such as 1,000 to 150,000 Da, such as 1,000 to 100,000 Da, such as 1,000 to 50,000 Da, or even 1,000 to 25,000 Da. Polyester materials can have Mn with a content of 2,000 to 250,000 Da, preferably 2,000 to 200,000 Da, such as 2,000 to 150,000 Da, such as 2,000 to 100,000 Da, such as 2,000 to 50,000 Da, or even 2,000 to 25,000 Da. Polyester materials can also have Mn with a content of 3,000 to 250,000 Da, preferably 3,000 to 200,000 Da, such as 3,000 to 150,000 Da, such as 3,000 to 100,000 Da, such as 3,000 to 50,000 Da, or even 3,000 to 25,000 Da. Polyester materials can have Mn with a content of 4,000 to 250,000 Da, preferably 4,000 to 200,000 Da, such as 4,000 to 150,000 Da, such as 4,000 to 100,000 Da, such as 4,000 to 50,000 Da, or even 4,000 to 25,000 Da. Polyester materials can also have Mn with a content of 5,000 to 250,000 Da, preferably 5,000 to 200,000 Da, such as 5,000 to 150,000 Da, such as 5,000 to 100,000 Da, such as 5,000 to 50,000 Da, or even 5,000 to 25,000 Da. Polyester materials can have Mn with a content of 6,000 to 250,000 Da, preferably 6,000 to 200,000 Da, such as 6,000 to 150,000 Da, such as 6,000 to 100,000 Da, such as 6,000 to 50,000 Da, or even 6,000 to 25,000 Da. Polyester materials can also have Mn with a content of 7,000 to 250,000 Da, preferably 7,000 to 200,000 Da, such as 7,000 to 150,000 Da, such as 7,000 to 100,000 Da, such as 7,000 to 50,000 Da, or even 7,000 to 25,000 Da.Polyester materials can have Mn with a content of 8,000 to 250,000 Da, preferably 8,000 to 200,000 Da, such as 8,000 to 150,000 Da, such as 8,000 to 100,000 Da, such as 8,000 to 50,000 Da, or even 8,000 to 25,000 Da. Polyester materials can also have Mn with a content of 9,000 to 250,000 Da, preferably 9,000 to 200,000 Da, such as 9,000 to 150,000 Da, such as 9,000 to 100,000 Da, such as 9,000 to 50,000 Da, or even 9,000 to 25,000 Da. Polyester materials can have Mn with a content of 10,000 to 250,000 Da, preferably 10,000 to 200,000 Da, such as 10,000 to 150,000 Da, such as 10,000 to 100,000 Da, such as 10,000 to 50,000 Da, or even 10,000 to 25,000 Da. Polyester materials can also have Mn with a content of 15,000 to 250,000 Da, preferably 15,000 to 200,000 Da, such as 15,000 to 150,000 Da, such as 15,000 to 100,000 Da, such as 15,000 to 50,000 Da, or even 15,000 to 25,000 Da.

[0114] Suitablely, the polyester material may have Mn of 5,000 to 25,000 Da.

[0115] As reported herein, Mn was determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11 (“Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography”. UV detector: 254 nm; solvent: unstabilized THF; residence time marker: toluene; sample concentration: 2 mg / ml). Unless otherwise specified, all Mn values ​​reported herein were measured in this manner.

[0116] Polyester materials can have any suitable weight-average molecular weight (Mw).

[0117] Polyester materials can have a molecular weight of at least 500 Daltons (Da = g / molar).

[0118] Polyester materials can have a Mw of at least 1000 Da.

[0119] Polyester materials can have a Mw of at least 2,000 Da.

[0120] Polyester materials can have a Mw of at least 3,000 Da.

[0121] Polyester materials can have a Mw of at least 4,000 Da.

[0122] Polyester materials can have a Mw of at least 5,000 Da.

[0123] Polyester materials can have a Mw of at least 6,000 Da.

[0124] Polyester materials can have a Mw of at least 7,000 Da.

[0125] Polyester materials can have a Mw of at least 8,000 Da.

[0126] Polyester materials can have a Mw of at least 9,000 Da.

[0127] Polyester materials can have a Mw of at least 10,000 Da.

[0128] Polyester materials can have a Mw of at least 15,000 Da.

[0129] Polyester materials can have a maximum Mw of 1,250,000 Da.

[0130] Polyester materials can have a maximum Mw of 1,000,000 Da.

[0131] Polyester materials can have a maximum Mw of 750,000 Da.

[0132] Polyester materials can have a maximum Mn content of 500,000 Da.

[0133] Polyester materials can have a maximum Mw of 250,000 Da.

[0134] Polyester materials can have a maximum Mw of 200,000 Da.

[0135] Polyester materials can have a maximum Mw of 150,000 Da.

[0136] Polyester materials can have a maximum Mw of 100,000 Da.

[0137] Polyester materials can have a maximum Mw of 50,000 Da.

[0138] Polyester materials can have a maximum Mw of 25,000 Da.

[0139] Polyester materials can have a Mw of 500 to 1,250,000 Da, suitably 500 to 1,000,000 Da, such as 500 to 750,000 Da, such as 500 to 500,000 Da, such as 500 to 250,000 Da, such as 500 to 200,000 Da, such as 500 to 150,000 Da, such as 500 to 100,000 Da, such as 500 to 50,000 Da, or even 500 to 25,000 Da. Polyester materials can have a Mw of 1,000 to 1,250,000 Da, suitably 1,000 to 1,000,000 Da, such as 1,000 to 750,000 Da, such as 1,000 to 500,000 Da, such as 1,000 to 250,000 Da, such as 1,000 to 200,000 Da, such as 1,000 to 150,000 Da, such as 1,000 to 100,000 Da, such as 1,000 to 50,000 Da, or even 1,000 to 25,000 Da. Polyester materials can have a Mw of 2,000 to 1,250,000 Da, suitably 2,000 to 1,000,000 Da, such as 2,000 to 750,000 Da, such as 2,000 to 500,000 Da, such as 2,000 to 250,000 Da, such as 2,000 to 200,000 Da, such as 2,000 to 150,000 Da, such as 2,000 to 100,000 Da, such as 2,000 to 50,000 Da, or even 2,000 to 25,000 Da. Polyester materials can have a Mw of 3,000 to 1,250,000 Da, suitably 3,000 to 1,000,000 Da, such as 3,000 to 750,000 Da, such as 3,000 to 500,000 Da, such as 3,000 to 250,000 Da, such as 3,000 to 200,000 Da, such as 3,000 to 150,000 Da, such as 3,000 to 100,000 Da, such as 3,000 to 50,000 Da, or even 3,000 to 25,000 Da. Polyester materials can have a Mw of 4,000 to 1,250,000 Da, suitably 4,000 to 1,000,000 Da, such as 4,000 to 750,000 Da, such as 4,000 to 500,000 Da, such as 4,000 to 250,000 Da, such as 4,000 to 200,000 Da, such as 4,000 to 150,000 Da, such as 4,000 to 100,000 Da, such as 4,000 to 50,000 Da, or even 4,000 to 25,000 Da.Polyester materials can have a Mw of 5,000 to 1,250,000 Da, suitably 5,000 to 1,000,000 Da, such as 5,000 to 750,000 Da, such as 5,000 to 500,000 Da, such as 5,000 to 250,000 Da, such as 5,000 to 200,000 Da, such as 5,000 to 150,000 Da, such as 5,000 to 100,000 Da, such as 5,000 to 50,000 Da, or even 5,000 to 25,000 Da. Polyester materials can have a Mw of 6,000 to 1,250,000 Da, suitably 6,000 to 1,000,000 Da, such as 6,000 to 750,000 Da, such as 6,000 to 500,000 Da, such as 6,000 to 250,000 Da, such as 6,000 to 200,000 Da, such as 6,000 to 150,000 Da, such as 6,000 to 100,000 Da, such as 6,000 to 50,000 Da, or even 6,000 to 25,000 Da. Polyester materials can have a Mw of 7,000 to 1,250,000 Da, suitably 7,000 to 1,000,000 Da, such as 7,000 to 750,000 Da, such as 7,000 to 500,000 Da, such as 7,000 to 250,000 Da, such as 7,000 to 200,000 Da, such as 7,000 to 150,000 Da, such as 7,000 to 100,000 Da, such as 7,000 to 50,000 Da, or even 7,000 to 25,000 Da. Polyester materials can have a Mw of 8,000 to 1,250,000 Da, suitably 8,000 to 1,000,000 Da, such as 8,000 to 750,000 Da, such as 8,000 to 500,000 Da, such as 8,000 to 250,000 Da, such as 8,000 to 200,000 Da, such as 8,000 to 150,000 Da, such as 8,000 to 100,000 Da, such as 8,000 to 50,000 Da, or even 8,000 to 25,000 Da. Polyester materials can have a Mw of 9,000 to 1,250,000 Da, suitably 9,000 to 1,000,000 Da, such as 9,000 to 750,000 Da, such as 9,000 to 500,000 Da, such as 9,000 to 250,000 Da, such as 9,000 to 200,000 Da, such as 9,000 to 150,000 Da, such as 9,000 to 100,000 Da, such as 9,000 to 50,000 Da, or even 9,000 to 25,000 Da.Polyester materials can have a Mw of 10,000 to 1,250,000 Da, suitably 10,000 to 1,000,000 Da, such as 10,000 to 750,000 Da, such as 10,000 to 500,000 Da, such as 10,000 to 250,000 Da, such as 10,000 to 200,000 Da, such as 10,000 to 150,000 Da, such as 10,000 to 100,000 Da, such as 10,000 to 50,000 Da, or even 10,000 to 25,000 Da. Polyester materials can have a Mw of 15,000 to 1,250,000 Da, suitably 15,000 to 1,000,000 Da, such as 15,000 to 750,000 Da, such as 15,000 to 500,000 Da, such as 15,000 to 250,000 Da, such as 15,000 to 200,000 Da, such as 15,000 to 150,000 Da, such as 15,000 to 100,000 Da, such as 15,000 to 50,000 Da, or even 15,000 to 25,000 Da.

[0140] Suitablely, the polyester material may have a Mw that is substantially equal to the Mn of the polyester or may have a maximum of five (5) times the Mn of the polyester material, such as a maximum of three (3) times the Mn of the polyester material.

[0141] As reported in this paper, Mw was determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11 (“Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography”. UV detector: 254 nm; solvent: unstabilized THF; residence time marker: toluene; sample concentration: 2 mg / ml).

[0142] Polyester materials can have any suitable total hydroxyl value (OHV).

[0143] Polyester materials can have a total OHV of at least 0 mg KOH / g.

[0144] Polyester materials can have an OHV of at least 5 mg KOH / g.

[0145] Polyester materials can have an OHV of at least 10 mg KOH / g.

[0146] Polyester materials can have an OHV of up to 150 mg KOH / g.

[0147] Polyester materials can have an OHV of up to 120 mg KOH / g.

[0148] Polyester materials can have an OHV of up to 110 mg KOH / g.

[0149] Polyester materials can have an OHV of up to 100 mg KOH / g.

[0150] Polyester materials can have an OHV of 0 to 150 mg KOH / g, preferably 0 to 120 mg KOH / g, such as 0 to 110 mg KOH / g, or even 0 to 100 mg KOH / g. Polyester materials can have an OHV of 5 to 150 mg KOH / g, preferably 5 to 120 mg KOH / g, such as 5 to 110 mg KOH / g, or even 5 to 100 mg KOH / g. Polyester materials can have an OHV of 10 to 150 mg KOH / g, preferably 10 to 120 mg KOH / g, such as 10 to 110 mg KOH / g, or even 10 to 100 mg KOH / g.

[0151] Where appropriate, the total hydroxyl value (OHV) is expressed as a solid.

[0152] As reported in this paper, the hydroxyl value is equivalent to the number of mg of KOH in 1 g of the substance. A solid polyester sample (0.13 g) was accurately weighed into an Erlenmeyer flask and dissolved in 20 mL of tetrahydrofuran using appropriate gentle heating and stirring. Then, 10 mL of 0.1 M 4-(dimethylamino)pyridine (catalyst solution) in tetrahydrofuran and 5 mL of 9 vol% acetic anhydride solution in tetrahydrofuran (i.e., 90 mL of acetic anhydride in 910 mL of tetrahydrofuran; acetylation solution) were added to the mixture. After 5 minutes, 10 mL of 80 vol% tetrahydrofuran solution (i.e., 4 parts by volume of tetrahydrofuran to 1 part distilled water; hydrolysis solution) was added. After 15 minutes, 10 mL of tetrahydrofuran was added and the solution was titrated with 0.5 M potassium hydroxide (KOH) ethanol solution. A blank sample was also run, where the solid polyester sample was omitted. The hydroxyl value is expressed in mg KOH / g and calculated using the following equation:

[0153]

[0154] Where V1 is the titer of the KOH solution (ml) for the polyester sample and V2 is the titer of the KOH solution (ml) for the blank sample. All total hydroxyl values ​​reported in this paper were measured in this manner.

[0155] Polyester materials can have any suitable acid value (AN).

[0156] Polyester materials can have an AN of at least 0 mg KOH / g.

[0157] Polyester materials can have an AN content of at least 5 mg KOH / g.

[0158] Polyester materials can have an AN of at least 10 mg KOH / g.

[0159] Polyester materials can have an AN of up to 150 KOH / g.

[0160] Polyester materials can have an AN of up to 100 mg KOH / g.

[0161] Polyester materials can have an AN of up to 50 mg KOH / g.

[0162] Polyester materials can have a KOH / g content of 0 to 150 mg, preferably 0 to 100 mg, such as AN with a KOH / g content of 0 to 50 mg. Polyester materials can have a KOH / g content of 5 to 150 mg, preferably 5 to 100 mg, such as AN with a KOH / g content of 5 to 50 mg. Polyester materials can have a KOH / g content of 10 to 150 mg, preferably 10 to 100 mg, such as AN with a KOH / g content of 10 to 50 mg.

[0163] Appropriately, acid value (AN) is expressed as a solid.

[0164] As reported herein, AN was determined by titration with 0.1 M potassium hydroxide (KOH) methanol solution. A solid polyester sample (typically 0.5 to 2.0 g) was accurately weighed into a 2 oz wide-mouth glass flask and dissolved appropriately in 25 mL of 3:1 (mass:mass) THF:1,3-propanediol or 4:1 (mass:mass) acetone:xylene using gentle heating and stirring. The solution was then cooled to room temperature and titrated with 0.1 M potassium hydroxide methanol solution. The endpoint of the titration was determined electronically by the amount of titrant required to induce an inflection point in the titration curve. Phenolphthalein indicator was added periodically as an alternative method to verify the equivalence point. The acid value was expressed in mg KOH / g and calculated using the following equation:

[0165]

[0166] All acid values ​​reported in this paper were measured in this manner.

[0167] Polyester materials may include reaction products comprising the following reaction mixtures:

[0168] (i) 1,2-propanediol,

[0169] (ii) terephthalic acid, and

[0170] (iii) Molecular weight enhancers

[0171] The polyester material has a number-average molecular weight (Mn) of at least 6,100 Da and a glass transition temperature (Tg) of at least 80°C. Further details of such polyesters are provided in European Patent Application Nos. EP 3074448 and EP3074447, the entire contents of each of which are incorporated herein by reference.

[0172] Polyester materials can be present in any suitable amount in the coating composition.

[0173] The coating composition may contain at least 10 wt% polyester material, based on the total solid weight of the coating composition.

[0174] The coating composition may contain at least 20 wt% polyester material, based on the total solid weight of the coating composition.

[0175] The coating composition may contain at least 30 wt% polyester material, based on the total solid weight of the coating composition.

[0176] The coating composition may contain at least 40 wt% polyester material, based on the total solid weight of the coating composition.

[0177] The coating composition may contain at least 50 wt% polyester material, based on the total solid weight of the coating composition.

[0178] The coating composition may contain at least 60 wt% polyester material, based on the total solid weight of the coating composition.

[0179] The coating composition may contain at least 70 wt% polyester material, based on the total solid weight of the coating composition.

[0180] The coating composition may contain up to 99 wt% polyester material, based on the total solid weight of the coating composition.

[0181] The coating composition may contain up to 95 wt% polyester material, based on the total solid weight of the coating composition.

[0182] The coating composition may contain up to 90 wt% polyester material, based on the total solid weight of the coating composition.

[0183] The coating composition may contain up to 80 wt% polyester material, based on the total solid weight of the coating composition.

[0184] The coating composition may contain 10 to 99 wt%, preferably 10 to 95 wt%, such as 10 to 90 wt%, or even 10 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 20 to 99 wt%, preferably 20 to 95 wt%, such as 20 to 90 wt%, or even 20 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 30 to 99 wt%, preferably 30 to 95 wt%, such as 30 to 90 wt%, or even 30 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 40 to 99 wt%, preferably 40 to 95 wt%, such as 40 to 90 wt%, or even 40 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 50 to 99 wt%, preferably 50 to 95 wt%, such as 50 to 90 wt%, or even 50 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 60 to 99 wt%, preferably 60 to 95 wt%, such as 60 to 90 wt%, or even 60 to 80 wt% of polyester material, based on the total solid weight of the coating composition. The coating composition may contain 70 to 99 wt%, preferably 70 to 95 wt%, such as 70 to 90 wt%, or even 70 to 80 wt% of polyester material, based on the total solid weight of the coating composition.

[0185] Suitably, the coating composition may contain 70 to 80 wt% polyester material, based on the total solid weight of the coating composition.

[0186] Polyester materials may include acrylic polyester resins. Acrylic polyester resins may include acrylic-modified polyester resins, which may be polyester materials with acrylic polymers grafted thereon.

[0187] Suitablely, acrylic polyester resins can be obtained by grafting acrylic polymers and polyester materials, wherein the polyester materials can be obtained by polymerizing the following:

[0188] i) Polybasic acid components, and

[0189] ii) Polyol components,

[0190] In this embodiment, one of the polyacid components or polyol components contains a functional monomer that is operable to impart a functional group to a polyester material, thereby allowing the acrylic polymer to be grafted onto the polyester material using the functional group.

[0191] The polyacid or polyol component of the acrylic polyester resin contains functional monomers operable to impart functional groups to the polyester material. These functional groups allow acrylic polymers to be grafted onto the polyester material via the use of said functional groups. The functional groups may include olefinic unsaturations, carboxylic acid functional groups, or epoxy functional groups. The functional groups may be in or attached to the backbone of the polyester material.

[0192] The functional monomer may include an olefinically unsaturated monomer that is operable to impart olefinically unsaturated functional groups to or from the backbone of the polyester material. Suitably, the functional group may include an olefinically unsaturated degree, which may be within the backbone of the polyester material.

[0193] Suitable functional monomers include: maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, medaconic acid, medaconic anhydride, phenylmaleic acid, phenylmaleic anhydride, tert-butylmaleic acid, tert-butylmaleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methylmaleic acid, methylmaleic anhydride and / or trimethylolpropane monoallyl ether.

[0194] When the functional monomer contains a polybasic acid, the functional monomer may be present in an amount of 0.5 to 10 wt%, suitably 1 to 5 wt%, based on the dry weight of the polybasic acid component.

[0195] When the functional monomer contains a polyol, the functional monomer may be present in an amount of 0.5 to 10 wt%, suitably 1 to 5 wt%, based on the dry weight of the polyol component.

[0196] Suitablely, the functional monomers of the acrylic polyester resin polyester material may include maleic acid, maleic anhydride and / or fumaric acid.

[0197] Suitable acrylic polyester resins are modified with acrylic substances by grafting acrylic-based modified polymers onto the polyester material. This grafting can occur via free radical polymerization, such as by free radical polymerization onto the olefinic unsaturation of the polyester material.

[0198] Suitably, the acrylic-modified polymer is formed from acrylic monomers. Suitably, the acrylic-modified polymer is grafted onto the polyester material by polymerizing the acrylic monomers in the presence of the polyester material to form an acrylic-modified polyester resin.

[0199] 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, and nitrs such as (meth)acrylonitrile. Any other acrylic monomers known to those skilled in the art can also be used. Conventionally and as used herein, the term "(meth)acrylate...ester" and similar terms refer to both methacrylate and acrylate. Suitable acrylic-modified polymers are formed from: methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methyl 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 phosphate).

[0200] Acrylic monomers may comprise a ratio of methacrylate monomers to acrylate monomers of at least 1:1, such as at least 2:1, at least 3:1, or at least 4:1, suitably at least 5:1. Acrylic monomers may be substantially free of acrylate monomers. The terms "methacrylate monomers" and "acrylate monomers" in relation to the proportions of these types of monomers in the acrylic monomers of the acrylic modified polymer refer to the total number of methacrylate monomers of all types forming the acrylic modified polymer relative to the total number of acrylate monomers. For example, if the acrylic modified polymer is formed from methyl methacrylate, methyl acrylate, and butyl acrylate, the amount of methyl methacrylate relative to the combined amount of methyl acrylate and butyl acrylate will be at least 5:1.

[0201] Acrylic monomers may include hydroxyl-functional monomers, such as hydroxyethyl (meth)acrylate. Suitably, the hydroxyl-functional monomer is present in an amount of 5 to 40 wt%, such as 5 to 30 wt% or 10 to 20 wt%, based on the dry weight of the acrylic modified polymer.

[0202] Acrylic-modified polymers may also contain a certain amount (0 to 30 wt%, based on the dry weight of the acrylic-modified polymer) of non-acrylic monomers. Such non-acrylic monomers may include other olefinically unsaturated monomers, such as styrene, ethylene, propylene, vinyltoluene, butadiene, 1-octene or isopentenene, and vinyl esters such as vinyl acetate.

[0203] It has been determined that acrylic-based modified polymers may suitably include methacrylic acid or acrylic acid to impart acid functional groups to the acrylic-based modified polymers. Suitably, the acid functional groups on the acrylic-based modified polymers can be at least partially neutralized with a neutralizing agent.

[0204] The Tg of acrylic-modified polymers (a measure of the Tg of acrylic-modified polymers polymerized as simple acrylic polymers in the absence of (or grafted onto) polyester resins) can range from 20 to 120°C. The Tg of acrylic-modified polymers can be calculated using the Fox equation provided in “Coatings of Polymers and Plastics”, Ryntz RA and Yaneff P. V, CRC Press, February 4, 2003, page 134.

[0205] Suitable neutralizing agents include ammonia or amine functional groups: methylethanolamine, dimethylethanolamine (DMEA), trimethylamine, and diethylenetriamine.

[0206] Suitably, at least 30% of the acid functional groups on the acrylic-modified polymer can be neutralized with a neutralizing agent. Suitably, at least 50% of the acid functional groups on the acrylic-modified polymer can be neutralized with a neutralizing agent. Suitably, at least 75% of the acid functional groups on the acrylic-modified polymer can be neutralized with a neutralizing agent.

[0207] Acrylic polyester resins can have any suitable acid value (AV). Acrylic polyester resins can have an AV of 10 to 80 KOH / g. Suitably, acrylic polyester resins can have a total AV of 20 to 70 mg KOH / g, such as 30 to 60 mg KOH / g. AV is suitably expressed on a solid basis.

[0208] Suitablely, the acrylic polyester resin is formed from polyester material and acrylic modified polymer in a weight ratio of 95 wt% to 55 wt% polyester material to 45 wt% to 5 wt% acrylic modified polymer, such as 90 wt% to 60 wt% polyester material to 40 wt% to 10 wt% acrylic modified polymer, or 85 wt% to 65 wt% polyester material to 35 wt% to 15 wt% acrylic modified polymer. For example, the acrylic polyester resin can be formed from polyester material and acrylic modified polymer in a weight ratio of 85 wt% polyester material to 15 wt% acrylic modified polymer.

[0209] When polyester materials contain sulfonated monomers, neutralization with acrylic polyester resins may not be necessary.

[0210] The coating composition can have any suitable Young's modulus. The coating composition can have a Young's modulus of 0.5 to 3 gigapascals (GPa), suitably 1.0 to 2.5 GPa, such as 1.5 to 2.0 GPa. Suitably, the coating composition can have a Young's modulus of 1.8 GPa.

[0211] The cured film formed from the coating composition may have a Young's modulus of ≥0.5 GPa, suitably ≥0.6 GPa, or ≥0.7 GPa, or ≥0.8 GPa, such as ≥0.9 GPa, ≥1.0 GPa, ≥1.1 GPa, ≥1.2 GPa, ≥1.3 GPa, ≥1.4 GPa or ≥1.5 GPa.

[0212] The Young's modulus reported in this paper was measured by tensile strength testing of a free membrane according to ASTM D2370-16 "Tensile Properties of Organic Coatings": sample size 122 mm x 12 mm x 10-20 µm; strain rate 20 mm / min; temperature 23°C. Advantageously, using a coating composition with a Young's modulus of 0.5 to 3 GPa implies that the coating composition has adequate tensile strength, such that it is substantially completely sheared in the area of ​​the notch line when the beverage can is opened. This helps to facilitate adequate venting.

[0213] The coating composition of the present invention can be a liquid coating composition or a powder coating composition.

[0214] It will be appreciated that the coating composition of the present invention is suitably formulated for application to can ends along the notch lines. Formation of the can ends may include applying the coating composition to a metal coil and curing the coating composition to form a cured film. The coated coil is then subjected to pressing, bending, and stamping to transform the coil into can ends. Therefore, the coating should be able to withstand these mechanical requirements. For example, the coating composition may have sufficient flexibility, adhesion to the substrate, hardness, and / or lubricity. The coating composition may contain a second polyester material in addition to the aforementioned polyester material.

[0215] The second polyester material may include any suitable polyester material. The second polyester material may include the reaction product of a polyacid and a polyol.

[0216] The second polyester material may suitably include organic polyacids.

[0217] The carboxylic acid groups of the polyacids in the second polyester material can be linked by bridging groups selected from the following: alkylene groups; alkenylene groups; ynylene groups; or arylene groups.

[0218] The second polyester material can be formed from any suitable polybasic acid. Suitable examples of polybasic acids include, but are not limited to, the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; selenic acid; glutaric acid; sebacic acid; dodecanoic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalenedicarboxylic acid; naphthalenetetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexanedicarboxylic acid; chlorobridged anhydride; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; tricyclodecane polycarboxylic acid; inner methylenetetrahydrophthalic acid; inner ethylhexahydrophthalic acid; cyclohexanetetracarboxylic acid; cyclohexanetetracarboxylic acid; esters and anhydrides of all the foregoing acids, and combinations thereof.

[0219] The second polyester material can be formed from diacids. The second polyester material can be formed from any suitable diacid. Suitable examples of diacids include, but are not limited to, the following: phthalic acid; isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebaceous acid; fumaric acid; 2,6-naphthalenedicarboxylic acid; phthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; diesters, such as dimethyl ester derivatives, for example, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, dimethyl fumarate, dimethyl phthalate, dimethyl succinate, dimethyl glutarate, dimethyl adipate; esters and anhydrides of all the aforementioned acids; and mixtures thereof.

[0220] Suitablely, the diacid of the second polyester material may include isophthalic acid, phthalic acid, maleic anhydride, and combinations thereof.

[0221] Suitablely, the polyol in the second polyester material may include organic polyols.

[0222] The second polyester material can be formed from any suitable polyol. Suitable examples of polyols include, but are not limited to, the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycols, including 1,2-propanediol; 1,3-propanediol; butyl ethyl propylene glycol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; butanediols, including 1,4-butanediol; 1,3-butanediol; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 2-ethyl-1,4-butanediol; pentanediols, including trimethylpentanediol and 2-methylpentanediol; cyclohexanediol; hexanediols, including 1,6-hexanediol; caprolactone diol (e.g., The reaction product of ε-caprolactone and ethylene glycol; hydroxyalkylated bisphenols; polyether glycols, such as poly(oxytetramethylene) glycol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; dimethylolcyclohexane; glycerol, etc., or combinations thereof.

[0223] The second polyester material can be formed from a diol. The second polyester material can be formed from any suitable diol. Suitable examples of 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; 2,2,4,4-Tetramethylcyclobutane-1,3-diol; Isosorbide; 1,4-Cyclohexanediol; 1,1'-Isopropylidene-bis(4-cyclohexanol); and mixtures thereof.

[0224] Suitably, the diol of the second polyester material may include 2-methyl-1,3-propanediol, cyclohexanediol, and combinations thereof.

[0225] The second polyester material may optionally be formed from additional monomers. The second polyester material may optionally include additional monomers selected from monobasic acids or monohydric alcohols or combinations thereof. Suitably, the optional additional monomers of the second polyester material may be organic.

[0226] The second polyester material may optionally be formed from another monobasic acid. The monobasic acid of the second polyester is preferably an organic monobasic acid.

[0227] The second polyester material may optionally be formed from any other suitable monobasic acid. Suitable examples include, but are not limited to, the following: 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 aforementioned acids and combinations thereof.

[0228] The second polyester material may optionally be formed from another monohydric alcohol. Preferably, the monohydric alcohol of the second polyester material is an organic monohydric alcohol.

[0229] The second polyester material may optionally be formed from any other suitable monohydric alcohol. Suitable examples include, but are not limited to, the following: benzyl alcohol; hydroxyethoxybenzene; methanol; ethanol; propanol; butanol; pentanol; hexanol; heptanol; dodecyl alcohol; stearyl alcohol; oleyl alcohol; undecyl alcohol; cyclohexanol; phenol; benzyl alcohol; methylbenzyl alcohol; cresol; monoethers of diols; halogen-substituted or other substituted alcohols and combinations thereof.

[0230] The coating composition may include an adhesion promoter. The adhesion promoter may include an acidic polyester. The second polyester material may include an acidic polyester.

[0231] The adhesive accelerator, which may contain acidic polyester, may be added in an amount of 0.1 to 15 wt% (based on the dry weight of the coating composition), more preferably 2 to 12 wt% (based on the dry weight of the coating composition). The acidic polyester may be present in an amount of 4 to 10 wt% (based on the dry weight of the coating composition).

[0232] Acidic polyesters may comprise the reaction product of a polyester with a phosphorus-containing acid such as phosphoric acid. In this context, the polyester may have an Mn value of 2000 to 10,000. The polyester may have a hydroxyl value of 20 to 75. The polyester may have an acid value of 15 to 25.

[0233] Suitably, acidic polyesters may comprise solutions of copolymers having acidic groups with an acid value of 15 to 100 mg KOH / g. Examples of commercially available suitable acidic polyesters include BYK-4510 (commercially available from Byk Altana), PLUSOLIT H-PD (commercially available from Mäder), BORCHI GEN HMP-F, or BORCHI GEN HE (commercially available from OMG Borchers).

[0234] Suitably, acidic polyesters may comprise reaction products comprising a reaction mixture of the following:

[0235] (a) A precursor polyester resin, wherein the precursor polyester resin is a condensation polymer of the following:

[0236] (I) A polyol component comprising a mixture of diols and triols; and

[0237] (II) Contains a polyacid component of α-unsaturated polycarboxylic acids; and

[0238] (b) Phosphorus-containing acids.

[0239] The second polyester material can have any suitable glass transition temperature (Tg).

[0240] Suitablely, the second polyester material may have a glass transition temperature (Tg) of -20°C to 30°C, such as -10°C to 0°C.

[0241] Suitablely, the second polyester material may have Mn of 2,000 to 10,000 Da.

[0242] Suitablely, the second polyester may have Mn of 4,000 to 10,000 Da.

[0243] Suitablely, the second polyester material may have a Mw of 2,000 to 10,000 Da.

[0244] Suitablely, the second polyester may have a Mw of 4,000 to 10,000 Da.

[0245] Suitably, the second polyester material may have a Mw that is substantially equal to the Mn of the second polyester or may have a Mw that is up to five (5) times the Mn of the second polyester material, such as a Mw that is up to three (3) times the Mn of the second polyester material. The second polyester material may have any suitable total hydroxyl value (OHV).

[0246] Suitablely, the second polyester material may have an AN content of 15 to 25 mg KOH / g.

[0247] The coating composition may contain any suitable amount of a second polyester material.

[0248] The coating composition may contain at least 0.5 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0249] The coating composition may contain at least 1 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0250] The coating composition may contain at least 2 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0251] The coating composition may contain at least 3 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0252] The coating composition may contain up to 10 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0253] The coating composition may contain up to 8 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0254] The coating composition may contain up to 5 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0255] The coating composition may contain 0.5 to 5 wt%, suitably 1 to 5 wt%, such as 2 to 5 wt%, or even 3 to 5 wt%, of a second polyester material, based on the total solid weight of the coating composition.

[0256] Suitably, the coating composition may contain 3 to 5 wt% of a second polyester material, based on the total solid weight of the coating composition.

[0257] The first polyester material and the second polyester material can be present in the coating composition in any suitable weight ratio.

[0258] The weight ratio of the first polyester material to the second polyester material can be up to 99:1.

[0259] The weight ratio of the first polyester material to the second polyester material can be up to 97:3.

[0260] The weight ratio of the first polyester material to the second polyester material can be at least 80:20.

[0261] The weight ratio of the first polyester material to the second polyester material can be at least 90:10.

[0262] Suitablely, the weight ratio of the first polyester material to the second polyester material can be from 99:1 to 60:40.

[0263] Suitablely, the weight ratio of the first polyester material to the second polyester material can be from 99:1 to 95:5.

[0264] The coating composition may include crosslinking materials.

[0265] The coating composition may contain any suitable crosslinking material. Suitable crosslinking materials will be well known to those skilled in the art.

[0266] The crosslinking material can be operable to crosslink the polyester material.

[0267] Crosslinked materials can be single molecules, dimers, oligomers, (co)polymers, or mixtures thereof. Crosslinked materials can be dimers or trimers.

[0268] Suitable crosslinking materials include, but are not limited to, one or more of the following: phenolic resins (or phenol-formaldehyde resins); amino plastic resins (or triazine-formaldehyde resins); amino resins; epoxy resins; isocyanate resins; hydroxyl (alkyl)amide resins; alkylated urethane resins; polybasic acids; acid anhydrides; organometallic acid functional materials; polyamines; polyamides and combinations thereof.

[0269] Suitable examples of phenolic resins are those formed by the reaction of phenol with an aldehyde or ketone, preferably by the reaction of phenol with an aldehyde, such as the reaction of phenol with formaldehyde or acetaldehyde, or even those formed by phenol with formaldehyde. Non-limiting examples of phenols that can be used to form phenolic resins are phenol, butylphenol, xylenol, and cresol. A 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 have a fusible-soluble phenolic resin type. “Fusible-soluble phenolic resin type” means a resin formed in the presence of an alkaline (base) catalyst and optionally an excess of formaldehyde. Suitable examples of commercially available phenolic resins include, but are not limited to, those commercially available from Allnex under the trade name PHENODUR (RTM), such as PHENODUR EK-827, PHENODUR VPR1785, PHENODUR PR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODUR PR612, or PHENODUR PH2024; resins commercially available from Sumitomo Bakelite co., ltd. under the trade name BAKELITE (RTM), such as BAKELITE 6582 LB, BAKELITE 6535, BAKELITE PF9989, or BAKELITE PF6581; SFC 112, commercially available from SI Group; and DUREZ (RTM). 33356, commercially available from SHHPP; ARALINK (RTM) 40-852, commercially available from Bitrez; or combinations thereof.

[0270] Suitable examples of isocyanate resins include, but are not limited to, the following: isophorone diisocyanates (IPDI), such as those commercially available from Cevstro under the trade name DESMODUR (RTM), e.g., DESMODUR VP-LS2078 / 2 or DESMODUR PL 340, or those commercially available from Evonik under the trade name VESTANAT (RTM), e.g., VESTANANT B 1370, VESTANAT B 118 6A, or VESTANAT B 1358 A; blocked aliphatic polyisocyanates based on hexamethylene diisocyanate (HDI), such as those commercially available from Covestro under the trade name DESMODUR (RTM), e.g., DESMODUR BL3370 or DESMODUR BL 3175 SN, and those commercially available from AsahiKASEI under the trade name DURANATE (RTM), e.g., DURANATE MF-K60X, those commercially available from Vencorex Chemicals under the trade name TOLONATE (RTM), such as TOLONATE D2, or those commercially available from Baxenden under the trade name TRIXENE (RTM), such as TRIXENE-BI-7984 or TRIXENE7981; or combinations thereof.

[0271] 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.

[0272] Suitable crosslinking materials may include hydroxyalkylamide substances, such as β-hydroxyalkylamide substances.

[0273] Crosslinked materials may contain terminal chemical groups as shown in Formula I.

[0274]

[0275] Among them, R 10 Indicates electron-withdrawing groups, such as (=O); and

[0276] Y 1 and Y 2 Each can be represented independently as a C1 to C3 alkylene group.

[0277] The terminal chemical group of Formula I can be attached to another chemical structure not shown. Alternatively or additionally, the chemical group of Formula I can be suspended by a carrier substrate, such as a silica carrier substrate.

[0278] Crosslinked materials may contain multiple terminal chemical groups as shown in Formula I. For example, crosslinked materials may contain 2, 3, or 4 terminal chemical groups as shown in Formula I.

[0279] Crosslinked materials may include structural portions according to Formula II:

[0280]

[0281] Among them, R 10 and R 11 Each can independently represent an electron-withdrawing group, such as (=O);

[0282] Y 1 Y 2 Y 3 and Y 4 Each independently represents a C1 to C3 alkylene group; and

[0283] X represents a C2 to C6 alkylene group.

[0284] Appropriately, R 10 and R 11 Each of them represents an O group.

[0285] Suitablely, Y 1 Y 2 Y 3 and Y 4 Each of them represents an ethylene group.

[0286] Suitablely, X represents a butylene group.

[0287] Therefore, crosslinked materials may include materials of Formula III:

[0288]

[0289] Crosslinking materials may include commercially available β-hydroxyalkylamide crosslinking materials, such as PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N',N'-tetratetra(2-hydroxypropyl)hexamethylenediamide.

[0290] The crosslinking material can be in the form of a urea material. The crosslinking material can include hydroxyl-substituted urea materials. Suitably, the crosslinking material can include hydroxyl-functionalized alkyl polyurea materials.

[0291] Suitablely, hydroxyl-functionalized alkyl polyurea materials may include materials having the following formula:

[0292]

[0293] Wherein, R includes an isocyanurate structural portion, a biuret structural portion, an allophonate structural portion, a glycourea structural portion, a benzoguanamine structural portion, a polyetheramine structural portion, and / or a polymer structural portion different from polyetheramine and having a Mn of 500 or more; wherein each R1 is independently hydrogen, an alkyl group having at least one carbon atom, or an alkyl group having hydroxyl functionalization of two or more carbon atoms, and at least one R1 is an alkyl group having hydroxyl functionalization of two or more carbon atoms; and n is 2-6.

[0294] Suitablely, hydroxyl-functionalized alkyl polyurea materials may include materials having the following formula:

[0295]

[0296] Wherein, R2 is a substituted or unsubstituted C1 to C36 alkyl group, aromatic group, isocyanurate structural moiety, biuret structural moiety, urethane structural moiety, glycourea structural moiety, benzoguanamine structural moiety, polyetheramine structural moiety and / or a polymer structural moiety different from polyetheramine and having Mn of 500 or more; wherein each R1 is independently hydrogen, an alkyl group having at least 1 carbon, or a hydroxyl-functional alkyl group having 2 or more carbons, and at least one R1 is a hydroxyl-functional alkyl group having 2 or more carbons; and n is 2-6.

[0297] Further details of suitable hydroxyl-functionalized alkyl polyurea materials are disclosed in PCT patent application WO 2017 / 123955, the entire contents of which are incorporated herein by reference.

[0298] Suitable examples of amino plastic resins include those formed by reacting triazines such as melamine or benzoguanidine with formaldehyde. Suitably, these condensation polymers can be etherified typically with methanol, ethanol, butanol, or mixtures thereof. For the chemistry, preparation, and uses of amino plastic resins, see “The Chemistry and Applications of AminoCrosslinking agents or Aminoplast,” Volume V, Part 11, page 21 and thereafter, edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998. Suitable examples of commercially available amino plastic resins include, but are not limited to, those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL MF980 (commercially available from Ineos); those sold under the trade name CYMEL (registered trademark), such as CYMEL303 and CYMEL 1128 (available from Allnex Industries); and combinations thereof.

[0299] Crosslinking materials can be present in the coating composition in any suitable amount.

[0300] The coating composition may contain at least 0.5 wt% of crosslinking material, based on the total solid weight of the coating composition.

[0301] The coating composition may contain at least 1 wt% of crosslinking material, based on the total solid weight of the coating composition.

[0302] The coating composition may contain at least 5 wt% crosslinking material, based on the total solid weight of the coating composition.

[0303] The coating composition may contain at least 10 wt% crosslinking material, based on the total solid weight of the coating composition.

[0304] The coating composition may contain at least 15 wt% crosslinking material, based on the total solid weight of the coating composition.

[0305] The coating composition may contain at least 20 wt% crosslinking material, based on the total solid weight of the coating composition.

[0306] The coating composition may contain up to 70 wt% crosslinking material, based on the total solid weight of the coating composition.

[0307] The coating composition may contain up to 60 wt% crosslinking material, based on the total solid weight of the coating composition.

[0308] The coating composition may contain up to 50 wt% crosslinking material, based on the total solid weight of the coating composition.

[0309] The coating composition may contain up to 40 wt% crosslinking material, based on the total solid weight of the coating composition.

[0310] The coating composition may contain up to 30 wt% crosslinking material, based on the total solid weight of the coating composition.

[0311] The coating composition may contain up to 25 wt% of crosslinking material, based on the total solid weight of the coating composition.

[0312] The coating composition may contain up to 20 wt% crosslinking material, based on the total solid weight of the coating composition.

[0313] The coating composition may contain 0.5 to 90 wt%, or 1 to 90 wt%, suitably 1 to 80 wt%, such as 1 to 70 wt%, such as 1 to 60 wt%, such as 1 to 50 wt%, such as 1 to 40 wt%, such as 1 to 30 wt%, or even 1 to 25 wt% of crosslinking material, based on the total solid weight of the coating composition. The coating composition may contain 5 to 90 wt%, suitably 5 to 80 wt%, such as 5 to 70 wt%, such as 5 to 60 wt%, such as 5 to 50 wt%, such as 5 to 40 wt%, such as 5 to 30 wt%, or even 5 to 25 wt% of crosslinking material, based on the total solid weight of the coating composition. The coating composition may contain 10 to 90 wt%, suitably 10 to 80 wt%, such as 10 to 70 wt%, such as 10 to 60 wt%, such as 10 to 50 wt%, such as 10 to 40 wt%, such as 10 to 30 wt%, or even 10 to 25 wt%, or 5 to 20 wt% of crosslinking material, based on the total solid weight of the coating composition. The coating composition may contain 15 to 90 wt%, preferably 15 to 80 wt%, such as 15 to 70 wt%, such as 15 to 60 wt%, such as 15 to 50 wt%, such as 15 to 40 wt%, such as 15 to 30 wt%, or even 15 to 25 wt% of crosslinking material, based on the total solid weight of the coating composition. The coating composition may also contain 20 to 90 wt%, preferably 20 to 80 wt%, such as 20 to 70 wt%, such as 20 to 60 wt%, such as 20 to 50 wt%, such as 20 to 40 wt%, such as 20 to 30 wt%, or even 20 to 25 wt% of crosslinking material, based on the total solid weight of the coating composition.

[0314] Suitably, the coating composition may contain 15 to 25 wt% of crosslinking material, based on the total solid weight of the coating composition.

[0315] Suitable crosslinking materials may include amino plastic resins.

[0316] Crosslinked materials may contain materials according to formula (XIII)

[0317]

[0318] Wherein, R1 is hydrogen or alkyl (e.g., C1 to C2). 20 Alkyl), aryl (e.g., C4 to C5) 24 Aryl), aralkyl (such as C5 to C6) 25 Aryl group, or —NR6R7;

[0319] R2 to R7 are each independently hydrogen or alkyl (e.g., C1 to C7). 20 Alkyl), aryl (e.g., C4 to C5) 24 Aryl), aralkyl (such as C5 to C6) 25Aryl group) or -CHR8OR9;

[0320] R8 and R9 are each independently hydrogen or alkyl (e.g., C1 to C9). 20 Alkyl), aryl (e.g., C4 to C5) 24 Aryl), aralkyl (such as C5 to C6) 25 Araneyl groups), alkoxyalkyl groups (such as C2 to C4) 40 alkoxyalkyl) or alkylaryl (such as C5 to C6) 25 Alkyl);

[0321] Wherein, at least one of R2 to R5 or R2 to R7 when present is -CHR8OR9, and suitably all of R2 to R5 or R2 to R7 when present is -CHR8OR9.

[0322] Suitably, in the crosslinked material according to formula (XIII), R1 is C1 to C2. 20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Aryl alkyl group, or —NR6R7; such as C4 to C5 24 Aryl or C5 to C 25 Aryl groups, or C4 to C5 24 Aryl, preferably C4 to C 12 Aryl, such as C6 aryl.

[0323] In the crosslinked material according to formula (XIII), R1 can be —NR6R7.

[0324] In the crosslinked material according to formula (XIII), R2 to R7 (where applicable) can each independently be hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl or -CHR8OR9; such as hydrogen, C1 to C 20 Alkyl groups or —CHR8OR9, such as hydrogen, C1 to C 10 Alkyl or -CHR8OR9; such as C1 to C5 alkyl or -CHR8OR9, preferably -CHR8OR9.

[0325] In the crosslinked material according to formula (XIII), R2 to R7 (where applicable) can each independently be hydrogen, C1 to C 20 Alkyl, C4 to C 24 Aryl or -CHR8OR9; such as hydrogen, C1 to C 20 Alkyl groups or —CHR8OR9, such as hydrogen, C1 to C 10 Alkyl or -CHR8OR9; such as C1 to C5 alkyl or -CHR8OR9, suitably -CHR8OR9, and R8 may independently be hydrogen, C1 to C20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Aryl alkyl, alkoxyalkyl C2 to C 40 alkoxyalkyl or C5 to C6 25 Alkyl aryl groups, such as hydrogen, C1 to C2 20 Alkyl, preferably hydrogen; and R9 can be hydrogen, C1 to C1. 20 Alkyl, C4 to C 24 Aryl, C5 to C 25 Aryl alkyl, alkoxyalkyl C2 to C 40 alkoxyalkyl or C5 to C6 25 Alkyl aryl; such as hydrogen, C1 to C 20 Alkyl; suitably, C1 to C1 20 Alkyl, or C1 to C 10 Alkyl, or C1 to C5 alkyl, such as C1 or C2 alkyl.

[0326] Crosslinking materials according to formula (XIII) can be formed by reacting triazine, such as melamine or benzoguanidine, with formaldehyde. Suitably, these condensates can be etherified typically with methanol, ethanol, butanol, or mixtures thereof. For the chemistry, preparation, and uses of amino plastic resins, see “The Chemistry and Applications of AminoCrosslinking agents or Aminoplast,” Volume V, Part 11, pp. 21 and up, edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998.

[0327] The crosslinking material according to formula (XIII) may include melamine or its derivatives, such as butylated and / or methylated melamine; and / or benzoguanamine or its derivatives, such as butylated and / or methylated benzoguanamine. Suitably, the crosslinking material according to formula (XIII) may include benzoguanamine or its derivatives, such as butylated and / or methylated benzoguanamine.

[0328] The crosslinking material according to formula (XIII) can form at least 50 wt% of the crosslinking material of the coating composition, such as at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 98 wt%, such as at least 99 wt% of the crosslinking material of the coating composition.

[0329] Suitablely, the crosslinking material may include those formed by reacting triazines, such as melamine or benzoguanamine, with formaldehyde.

[0330] Suitable crosslinking materials may include benzoguanidine or derivatives thereof.

[0331] Benzoguanidine or its derivatives may include commercially available benzoguanidine or its derivatives. Suitable examples of commercially available benzoguanidine and its derivatives include, but are not limited to, benzoguanidine-formaldehyde-based materials, such as those sold under the trade name CYMEL (registered trademark), such as CYMEL 1123 (commercially available from Allnex Industries); those sold under the trade name ITAMIN (registered trademark), such as ITAMIN BG143 (commercially available from Galstaff Multiresine); or those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL BF892 and MAPRENAL BF 892 / 68B (commercially available from Ineos); glycourea-based materials, such as those under the trade name CYMEL (registered trademark), such as CYMEL 1170 and CYMEL 1172 (commercially available from Allnex); and combinations thereof.

[0332] Suitablely, benzoguanidine or its derivatives may include benzoguanidine-formaldehyde-based materials sold under the trade name MAPRENAL (registered trademark).

[0333] Suitablely, benzoguanidine or its derivatives may include MAPRENAL BF892 and / or MAPRENAL BF 892 / 68B (commercially available from Ineos). Suitablely, benzoguanidine or its derivatives may include MAPRENAL BF 892 / 68B (commercially available from Ineos).

[0334] Suitably, the coating composition may contain 15 to 25 wt% benzoguanamine or its derivatives, based on the total solid weight of the coating composition.

[0335] The coating composition may additionally contain a solvent. The coating composition may include a single solvent or a mixture of solvents. The solvent may include water, an organic solvent, a mixture of water and an organic solvent, or a mixture of organic solvents.

[0336] The organic solvent suitably has sufficient volatility to evaporate substantially completely from the coating composition during the curing process. As a non-limiting example, the curing process can be performed by heating at 260 to 425°C for 5 to 20 seconds.

[0337] Suitable organic solvents include, but are not limited to, the following: aliphatic hydrocarbons such as solvent oils and high flash point naphtha; aromatic hydrocarbons such as benzene; toluene; xylene; solvent naphtha 100, 150, 200; those available from Exxon-Mobil Chemical Company under the trade name SOLVESSO (RTM); alcohols such as ethanol; n-propanol; isopropanol; and n-butanol; ketones such as acetone; cyclohexanone; methyl isobutyl ketone; methyl ethyl ketone; esters such as ethyl acetate; butyl acetate; n-hexyl acetate; RHODIASOLV (RTM) RPDE (a blend of succinate and adipate esters commercially available from Solvay); diols such as butyl ethylene glycol; glycol ethers such as methoxypropanol; ethylene glycol monomethyl ether; ethylene glycol monobutyl ether and combinations thereof. When present, the solvent may suitably be used in the coating composition in an amount of 5 to 90 wt%, preferably 10 to 80 wt%, such as 20 to 75 wt%, or even 30 to 70 wt%, based on the total weight of the coating composition. When present, the solvent may suitably be used in the coating composition in an amount of 50 to 70 wt%, based on the total weight of the coating composition.

[0338] The polyester materials of the present invention can be dissolved or dispersed in the solvent during and / or after their formation.

[0339] The coating composition may additionally contain a catalyst. Any catalyst typically used to catalyze the crosslinking reaction between polyester materials and crosslinking agents can be used. Suitable catalysts will be well known to those skilled in the art. The catalyst can be a nonmetallic or metallic catalyst or a combination thereof. Suitable nonmetallic catalysts include, but are not limited to, the following: phosphoric acid; blocked phosphoric acid; CYCAT (RTM) XK 406 N (commercially available from Allnex); sulfuric acid; sulfonic acid; CYCAT 600 (commercially available from Allnex); NACURE (RTM) 5076 or NACURE 5925 (commercially available from King Industries); acid phosphate catalysts, such as NACURE XC 235 (commercially available from King Industries); and combinations thereof. Suitable metallic catalysts will be well known to those skilled in the art. Suitable metal catalysts include, but are not limited to, the following: tin-containing catalysts, such as monobutyltin tri(2-ethylhexanoate); zirconium-containing catalysts, such as KKAT (RTM) 4205 (commercially available from King Industries); titanate-based catalysts, such as tetrabutyl titanate (TnBT) (commercially available from Sigma Aldrich); and combinations thereof. When present, the catalyst may be used in any suitable amount in the coating composition. When present, the catalyst may be used in amounts from 0.001 to 10 wt%, suitably from 0.001 to 5 wt%, such as 0.01 to 5 wt%, or even 1 to 3 wt%, based on the total solid weight of the coating composition. Suitably, when present, the catalyst may be used in amounts from 0.01 to 1.5 wt%, based on the total solid weight of the coating composition.

[0340] Suitable examples of catalysts, such as those for compositions containing acrylic polyester resins, may include, but are not limited to, the following: metal compounds, such as stannous octoate; stannous chloride; butylstannic acid (hydroxybutyltin oxide); monobutyltin tri(2-ethylhexanoate); chlorobutyltin dihydroxide; tetrapropyl titanate; tetrabutyl titanate; zinc acetate; acid compounds, such as phosphoric acid; p-toluenesulfonic acid; dodecylbenzenesulfonic acid (DDBSA), such as blocked DDBSA; tetraalkylzirconium compounds; antimony trioxide; germanium dioxide; and combinations thereof. Catalysts may include dodecylbenzenesulfonic acid (DDBSA), such as blocked DDBSA.

[0341] The catalyst may be present in the coating composition in an amount of 0.001 to 1%, suitably 0.01 to 0.7%, such as 0.025 to 0.5% of the dry weight of the aqueous coating composition or powder coating composition.

[0342] The coating composition may include additional resin materials. Suitable additional resin materials will be well known to those skilled in the art. Suitable examples of 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.

[0343] The coating composition may contain 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 carriers, lubricants, waxes and other conventional excipients.

[0344] 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 may be added to a coating composition in any suitable form, such as discrete particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants may be used in the coatings of the present invention. Suitable colorants are listed in U.S. Patent No. 8,614,286, column 7, lines 2 through 8, line 65, which is incorporated herein by reference. Suitable for packaging coatings are those approved for contact with food, such as titanium dioxide; iron oxides, such as iron oxide black; aluminum paste; aluminum powder, such as aluminum flakes; carbon black; ultramarine blue; phthalocyanines, such as phthalocyanine blue and phthalocyanine green; chromium oxides, such as chromium oxide green; graphite fibrils; ferried yellow; quindo red; and combinations thereof, as well as those listed in Code of Federal Regulations 178.3297, which is incorporated herein by reference. When present, the colorant may be used in the coating composition in any suitable amount. When present, the colorant may be used in the coating composition in an amount of up to 90 wt%, such as up to 50 wt%, or even up to 10 wt%, based on the total solid weight of the coating composition.

[0345] Suitable lubricants will be well known to those skilled in the art. Suitable examples of lubricants include, but are not limited to, the following: carnauba wax and polyethylene-type lubricants. When present, the lubricant may be used in the coating composition in an amount of at least 0.01 wt%, based on the total solid weight of the coating composition.

[0346] Surfactants may optionally be added to the coating composition to facilitate flow and substrate wetting. Suitable surfactants will be well known to those skilled in the art. When present, surfactants are suitably selected to be compatible with food and / or beverage container applications. Suitable surfactants include, but are not limited to, the following: alkyl sulfates (e.g., sodium lauryl sulfate); ether sulfates; phosphate (salt) esters; sulfonates; and various alkali metal, ammonium, and amine salts thereof; aliphatic alcohol ethoxylates; alkylphenol ethoxylates (e.g., nonylphenol polyether); salts and / or combinations thereof. When present, surfactants may be present in amounts from 0.01 wt% to 10 wt%, suitably from 0.01 to 5 wt%, such as from 0.01 to 2 wt%, based on the total solid weight of the coating composition.

[0347] The coating composition may be substantially free of, substantially free of, or completely free of bisphenol A (BPA) and its derivatives. Derivatives of BPA include, for example, bisphenol A diglycidyl ether (BADGE). The coating composition may be substantially free of or completely free of bisphenol F (BPF) and its derivatives. Derivatives of BPA include, for example, bisphenol F diglycidyl ether (BPFG). The compounds mentioned above or their derivatives may not have been intentionally added to the coating composition, but may be present in trace amounts due to unavoidable environmental contamination. "Substantially free" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the compounds mentioned above or their derivatives. "Substantially free" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the compounds mentioned above or their derivatives. "Completely free" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the compounds mentioned above or their derivatives.

[0348] Polyester materials and / or coating compositions may be substantially free of, substantially free of, or completely free of bisphenol A (BPA) and its derivatives. Derivatives of BPA include, for example, bisphenol A diglycidyl ether (BADGE). Polyester materials and / or coating compositions may be substantially free of or completely free of bisphenol F (BPF) and its derivatives. Derivatives of BPF include, for example, bisphenol F diglycidyl ether (BPFG). The compounds mentioned above or their derivatives may not have been intentionally added to the coating composition, but may be present in trace amounts due to unavoidable environmental contamination. "Substantially free" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the compounds mentioned above or their derivatives. "Substantially free" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the compounds mentioned above or their derivatives. "Completely free" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the compounds mentioned above or their derivatives.

[0349] Polyester materials and / or coating compositions may be substantially free of, substantially free of, or completely free of dialkyltin compounds, including 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" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the compounds mentioned above or their derivatives. "Substantially free of" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the compounds mentioned above or their derivatives. "Completely free of" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the compounds mentioned above or their derivatives.

[0350] Polyester materials and / or coating compositions may be substantially styrene-free. Coating compositions may be substantially styrene-free or may be completely styrene-free. "Substantially styrene-free" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the aforementioned compounds or their derivatives. "Substantially styrene-free" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the aforementioned compounds or their derivatives. "Completely styrene-free" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the stated compounds or their derivatives.

[0351] Polyester materials and / or coating compositions may be substantially phenol-free, substantially phenol-free, or completely phenol-free. "Substantially phenol-free" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the aforementioned compounds or their derivatives. "Substantially phenol-free" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the aforementioned compounds or their derivatives. "Completely phenol-free" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the stated compounds or their derivatives.

[0352] The polyester materials and / or coating compositions are substantially free of formaldehyde, or suitably substantially free of formaldehyde, or suitably completely free of formaldehyde. "Substantially free of formaldehyde" is intended to refer to polyester materials and / or coating compositions containing less than 1000 ppm of any of the compounds mentioned above or their derivatives. "Substantially free of formaldehyde" is intended to refer to polyester materials and / or coating compositions containing less than 100 ppm of any of the compounds mentioned above or their derivatives. "Completely free of formaldehyde" is intended to refer to polyester materials and / or coating compositions containing less than 20 ppb of any of the compounds mentioned above or their derivatives.

[0353] Polyester materials, coating compositions, and / or cured films derived from coating compositions may exclude 2,2,4,4-tetramethyl-1,3-cyclobutanediol (“TMCD”). The definition of monomers that increase Tg may exclude 2,2,4,4-tetramethyl-1,3-cyclobutanediol (“TMCD”). The definition of polyol components and / or diol components may exclude 2,2,4,4-tetramethyl-1,3-cyclobutanediol (“TMCD”).

[0354] The coating compositions of the present invention can have any suitable solids content. The coating compositions can have a solids content of 10 to 60% by weight of the coating composition, such as 15 to 50 wt% or suitably 20 to 40 wt%.

[0355] The coating compositions of the present invention can be cured by any suitable method. They can be cured by heat curing or by chemical curing, preferably by heat curing. The coating compositions can be cured at any suitable temperature during heat curing. The coating compositions can be cured to a peak metal temperature (PMT) of 150 to 350°C, preferably 175 to 320°C, such as 190 to 300°C, or even 200 to 280°C. Suitablely, the coating compositions can be cured at 210°C or 260°C during heat curing. For the avoidance of ambiguity, unless otherwise stated, the term "peak metal temperature" and similar terms as used herein mean the maximum temperature reached through the metal substrate during exposure to heat during heat curing. In other words, the peak metal temperature (PMT) is the maximum temperature reached through the metal substrate and not the temperature applied to it. Those skilled in the art will appreciate that the temperature reached through the metal substrate can be lower than or substantially equal to the temperature applied to it. Suitablely, the temperature reached through the metal substrate can be lower than the temperature applied to it.

[0356] The coating compositions of the present invention may have any suitable solids content. The coating compositions may have a solids content of 10 to 60% by weight, such as 15 to 50 wt%, or suitably 20 to 40 wt%.

[0357] The coating compositions of the present invention can be cured by any suitable method. They can be cured by thermal curing or chemical curing, preferably by thermal curing. The coating compositions can be cured at any suitable temperature during thermal curing. The coating compositions can be cured at temperatures ranging from 50 to 350°C, preferably 100 to 320°C, such as 150 to 300°C, or even 200 to 300°C during thermal curing. Suitablely, the coating compositions can be cured at 230°C or 250°C during thermal curing. Suitablely, the coating compositions can be cured to a peak metal temperature (PMT) of 230°C to 250°C during thermal curing. For the avoidance of ambiguity, unless otherwise stated, the term "peak metal temperature" and similar terms as used herein mean the maximum temperature reached by the metal substrate during exposure to heat during thermal curing. In other words, the peak metal temperature (PMT) is the maximum temperature reached by the metal substrate and not the temperature applied to it. Those skilled in the art will appreciate that the temperature reached by the metal substrate can be lower than or substantially equal to the temperature applied to it. Suitablely, the temperature achieved through the metal substrate can be lower than the temperature applied to it.

[0358] The coating composition of the present invention is cured to form a cured film.

[0359] A can may include a can body and can ends. Examples of cans include, but are not limited to, one or more of the following: two-piece cans, three-piece cans, etc. The can may be a beverage can.

[0360] The can can be formed from any suitable material. Suitable metals will be well known to those skilled in the art. Suitable examples include, but are not limited to, the following: steel; tinplate; tinplate pretreated with a protective material such as chromium, titanium, titanate, or aluminum; tin-free steel (TFS); galvanized steel, such as electroplated steel; aluminum; aluminum alloys; and combinations thereof. Those skilled in the art will appreciate that the body and end of a beverage can can be formed from the same or different materials, such as the same or different metals. Suitablely, the body and end of a beverage can can be formed from the same material, such as the same metal.

[0361] The can body and / or can end can be made of wound metal material. Suitably, at least the can end can be formed of wound metal material. Suitably, the coating composition of the present invention can be applied to wound metal material, such as wound metal material forming the can end (“can end material”).

[0362] The coating composition can be applied to the can end material, then the can end is cut and stamped from the wound metal material. The can end can be coated on one or both surfaces. Therefore, the can roll material can be coated on one or both surfaces, then the can end is cut and stamped from the wound metal material.

[0363] Advantageously, coating on both surfaces of the wound metal material can provide sufficient lubrication so that the coating can withstand the stamping operation.

[0364] The end of a can with a scoring line on it can be an "easy-open" can end, sometimes called an "easy-open end" or even an "EOE".

[0365] Suitablely, after the can end is punched out of the coated metal material, a scoring line is applied to the can end.

[0366] Once formed, the can end is suitably attached to the can body. The can end can be attached to the can body by any suitable method. Suitably, the can end can be attached to the can body by a crimping process.

[0367] The coating composition can be applied to at least the inner surface of the can end along a portion of the score line, or it can be applied along the entire score line.

[0368] The coating composition can be applied to substantially all or a portion of the inner surface of the can end, provided that the coating composition is applied to at least a portion of the inner surface of the can end along at least a portion of the score lines. Suitably, the coating composition can be applied to substantially all of the inner surface of the can end. The coating composition can be applied to at least a portion of the outer surface of the can end. The coating composition can be applied to substantially all or a portion of the outer surface of the can end. Suitably, the coating composition can be applied to at least a portion of the outer surface of the can end along at least a portion of the score lines. The coating composition can be applied to at least a portion of the inner and / or outer surfaces of the can body.

[0369] The coating composition can be applied to the beverage can by any suitable method. Methods for applying the coating composition will be well known to those skilled in the art. Suitable application methods include, but are not limited to, one or more of the following: spraying, roller coating, dip coating, and / or electrocoating.

[0370] The coating composition can be applied to any suitable dry film thickness. The coating composition can be applied to a dry film thickness of 0.1µm (micrometer) to 12µm, suitably 2µm to 8µm, more preferably 4µm to 7µm, or even 4µm to 6µm.

[0371] The coating composition can be applied to a beverage can as a single layer or as part of a multilayer system. The coating composition can be applied as a single layer. The coating composition can be applied as the first coating layer of a multilayer system. The coating composition can be applied as a base coat or primer. Second, third, fourth, and subsequent coatings can contain any suitable paint, such as those containing, for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins, or combinations thereof. The coating composition can be applied on top of another paint layer as part of a multilayer system. For example, the coating composition can be applied on top of a primer. The coating composition can form an intermediate layer or a top coating. The coating composition can be applied to the substrate once or multiple times. Those skilled in the art will appreciate that the body and ends of the beverage can can be coated independently with a single-layer or multilayer system.

[0372] As used in this article, “powder” and similar terms refer to materials in the form of solid particles, as opposed to materials in the form of liquids.

[0373] The powder coating composition of the present invention can be applied by any suitable method. Methods for applying the powder coating composition will be well known to those skilled in the art. Suitable application methods include, for example, electrostatic spraying, or application by supercorona discharge. Suitably, the powder coating composition according to the present invention can be applied by supercorona discharge.

[0374] When the substrate is conductive, the powder coating composition is typically applied electrostatically. Electrostatic spraying application generally involves drawing the coating composition from a fluidized bed and propelling it through a corona field. As the coating composition passes through the corona field, the particles become charged and are attracted to and deposited on the grounded conductive substrate. As charged particles begin to accumulate, the substrate becomes insulating, thus limiting the deposition of further particles.

[0375] 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 a dry film thickness of 0.1µm (micrometer) to 1000µm, suitably 3µm to 500µm, such as 5µm to 250µm, or even 5µm to 150µm, such as 10µm to 100µm.

[0376] The powder components of the present invention can have an average particle size of less than 15 micrometers (µm). The powder components can have an average particle size of 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 ambiguity, the term "less than" includes particles having the indicated average particle size. For example, "less than 15 µm" refers to particles having an average particle size of 15 µm as well as particles having an average particle size lower than that value.

[0377] Particles of these sizes can be prepared by any suitable method. Suitable methods will be well known to those skilled in the art. Examples of suitable methods include, but are not limited to, cold grinding, milling, and sieving methods.

[0378] 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 ambiguity, the term "dispersion" herein refers to powder suspended in a liquid. The coating composition may contain any suitable liquid carrier. The liquid carrier may contain 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 contain water.

[0379] It should be recognized that the term "inner surface of the can end" refers to the surface of the can end on the inside of the beverage can once the beverage can is attached, that is, the surface of the can end that will form the inner surface of the beverage can once the beverage can is attached.

[0380] As used herein, unless otherwise expressly indicated, all figures, such as those representing values, ranges, quantities, or percentages, may be understood as if they begin with the word “about,” even if the term is not explicitly stated. Similarly, any numerical range described herein is intended to include all subranges contained therein. The singular includes the plural, and vice versa. For example, although references herein include “a” coating composition, “a” polyester material, “a” aromatic polyacid, “the” polyester material, etc., may be used for one or more of these and any other components. The reference “one of the polyacid component or polyol component contains a functional monomer” means one or both of the polyacid component and / or polyol component containing a functional monomer. As used herein, the term “polymer” means both oligomers and homopolymers and copolymers, and the prefix “poly” means two or more. The terms “include, for example” and “similar” are intended to include, but are not limited to, examples.

[0381] All the features contained in this article can be combined with any of the above aspects and in any combination.

[0382] Plate preparation and testing methods

[0383] The following test plate preparation and testing methods were used in these embodiments:

[0384] Test plate preparation: Coated samples were coated onto zirconium-treated aluminum (0.0082 inches) using a wire-wound rod to produce a dry film weight of 6.5–7.5 mg / m² (msi). The plates were then baked in a three-zone coil oven (249 / 326 / 293°C) to a peak metal temperature of 240°C. The coated plates were then stamped and etched into CDL-type can ends.

[0385] Liquor 85 test kit (L-85): Prepare the L-85 stock solution as follows:

[0386]

[0387] 47 g of L-85 stock solution was added to a 12 oz aluminum beverage can, followed by 308 g of carbonated water (also known as effervescent water). A CDL seam machine was then used to attach the can end to the can body. The can was then placed upside down in a 38°C incubator for 10 days. After 10 days, the can was removed from the incubator and punctured from the bottom to empty the liquid. The can was then cut 10 mm below the neck area. The enamel rating of the end was then measured using the Waco Enamel Rater test described below. An acceptable enamel rating after L-85 package testing is less than 10 mA, preferably less than 5 mA.

[0388] WACO Enamel Rater Test: The WACO Enamel Rater test determines the integrity of the manufactured can end by quantifying metal exposure. The end is secured to an electrolyte-filled end clamp containing electrodes using a vacuum. The clamp and sample are inverted so that the product side of the electrodes and end is in contact with the electrolyte solution, and the edge of the sample is in contact with the metal chisel, ensuring a complete circuit. The instrument then applies a contact voltage (6.3 volts, DC) across the coated surface and measures the resulting current (mA) over an industry standard time of 4 seconds. The reading is proportional to the amount of exposed metal in the test sample. A low reading is desirable, as this indicates very little exposed metal at the end.

[0389] Outward Flank Test: The outward flank test is used to determine the degree of venting. The contents of a 12-ounce (340g) soda can, cooled overnight to 1.5°C, are gently transferred to an empty 12-ounce (340g) beverage can. The can end is then joined to the can body using a CDL seam machine. The can is placed upside down (i.e., with the end of the can being tested at the bottom) in an incubator and incubated at 38°C for 18 hours. After this, the can is removed from the incubator and transferred to a fume hood. The can end is then gently pulled with a lever using a can opener or screwdriver. If a metallic cracking sound (scratch line breaking) is heard during pressure release, there is no outward flank and sufficient venting has occurred. This is considered a pass. If a metallic cracking sound (scratch line breaking) is heard but no pressure is released, there is no outward flank and insufficient venting has occurred. This is considered a failure. The test is repeated multiple times, and the number of failures is recorded. For example, there were 2 failures out of 16 test repetitions, recorded as 2 / 16.

[0390] Glass transition temperature (Tg): Tg of polyester and coatings was measured using a Perkin Elmer differential scanning calorimeter at a heating rate of 10°C / min using differential scanning calorimetry (DSC). The sample was placed in the machine and heated from 30°C to 180°C, followed by a cooling slope from 180°C to -50°C. The sample was then reheated to 180°C. Tg data were determined by a second heating slope (i.e., from -50°C to 180°C). Tg values ​​were determined using machine software installed on the Perkin Elmer.

[0391] Instron analysis of Young's modulus: Instron analysis of free membranes (25.4 mm x 5 mm size) was performed at ambient temperature (24°C) using a small Instron 44 unit with a 50 N load cell and a rate of 5 mm / min. Each sample was measured 3–5 times to obtain representative results.

[0392] To better understand the present invention and demonstrate how embodiments of the invention can function, reference will now be made to the following experimental data by way of example.

[0393] Example

[0394] Solvent-based polyester examples

[0395] Comparative Polyester Example 1

[0396] Polyesters having the components in Table 1 are prepared according to the following method.

[0397] Components 1-4 were added to a 3L round-bottom flask equipped with a nitrogen blanket, temperature probe, Vigréux column, column temperature probe, and condenser. The flask was heated to carry out the transesterification reaction and to distill methanol, while maintaining a column temperature of 65°C and a maximum batch temperature of 230°C. Once the methanol distillation was complete, the flask was cooled to <150°C. Components 5-9 were added to the flask and heated to allow the reactants to esterify and transesterify, and to distill water. The resin was treated to a maximum of 230°C and maintained at a distillation temperature of 96°C. Once the resin acid value was <15.00 mg KOH / g, the flask was cooled to <160°C and component 10 was added. The Vigréux column and column temperature probe were then replaced with Dean-Stark (commercially available from Exxon Mobile) filled with SOLVESSO 100, thus converting the distillation to azeotropic distillation to remove water formed as a byproduct of the esterification reaction. Azeotropic distillation continued until an acid value <2.00 mg KOH / g and a viscosity (after dilution to 40% TNV in cyclohexanone) were achieved. Viscosity was measured according to ASTM D1545-89 ('Standard Test Method for Viscosity of Transparent Liquids by Bubble Time Method'). The resulting polyester material was then dissolved in components 11-14 to produce a resin with 42% by weight solids.

[0398] The glass transition temperature (Tg) of the obtained polyester is 31°C.

[0399] Table 1 – Composition of Comparative Polyester Example 1

[0400]

[0401] Commercially available from Exxon Mobile

[0402] Commercially available from Nexeo Solutions

[0403] Polyester Example 1

[0404] Under low-shear stirring, 801.50 g of Vylon GK880 (commercially available from Toyobo; a polyester with a number-average molecular weight Mn of 18,000 Da and a glass transition temperature Tg of 84°C) was slowly added to a stainless steel cup containing 666.77 g of cyclohexanone and 666.77 g of SOLVESSO 150 (commercially available from Exxon Mobile). Once all the Vylon GK880 had been added, the cup was covered and the stirring was increased to 2,000 rpm. The mixture was stirred at this high speed for 2.5 hours to completely dissolve the Vylon GK880.

[0405] Polyester Example 2

[0406] Polyester materials having the components shown in Table 2 are prepared according to the following method.

[0407] Add components 1-4 to a 5L round-bottom flask equipped with a nitrogen-coated atmosphere, temperature probe, Vigréux column, column temperature probe, and condenser. Heat the flask to carry out the esterification reaction and distill the water while maintaining a column temperature of 93°C and a maximum batch temperature of 235°C. Once the water distillation is complete, cool the flask to <150°C. Then add components 5-7 to the flask and replace the Vigréux column and column temperature probe with Dean-Stark solvent filled with SOLVESSO 100. Heat the flask to 200°C. Maintain azeotropic reflux to remove the water formed by the esterification reaction until the final viscosity (25°C, in 45% TNV, in cyclohexanone) and acid value <7.00 mg KOH / g, on a solids basis, are achieved at Z-Z1. Measure the viscosity according to ASTM D1545-89 ('Standard Test Method for Viscosity of Transparent Liquids by Bubble Time Method'). Determine the acid value as described above. The resulting polyester was then dissolved in components 8 and 9 to produce a composition with 42% by weight solids.

[0408] The glass transition temperature (Tg) of the obtained polyester is 78°C.

[0409] Table 2 – Composition of Polyester Example 2

[0410]

[0411] Commercially available from Exxon Mobile

[0412] Commercially available from Nexeo Solutions

[0413] Polyester Example 3

[0414] Under low-shear stirring, 854.00 g of Dynapol L912 granules (commercially available from Evonik; a polyester with a number-average molecular weight Mn of 15,000 Da and a glass transition temperature Tg of 105°C) were slowly added to a stainless steel cup containing 1281.00 g of SOLVESSO 150 (commercially available from Exxon Mobile). Once all the Dynapol L912 granules had been added, the cup was covered and the stirring was increased to 2,000 rpm. The mixture was stirred at this high speed for 2.5 hours to completely dissolve the Dynapol L912 granules.

[0415] Polyester Example 4

[0416] The phosphorylated polyester form of the adhesive accelerator having the components shown in Table 3 was prepared according to the following method.

[0417] Add components 1-6 to a 5L round-bottom flask equipped with a nitrogen-coated atmosphere, temperature probe, Vigréux column, column temperature probe, and condenser. Heat the flask to carry out the esterification reaction and distill the water while maintaining a column temperature of 96°C and a maximum batch temperature of 200°C. Once the water distillation is complete and the acid value is <13.00 mg KOH / g, cool the flask to <110°C and add components 7-9 to the flask. Then replace the Vigréux column and column temperature probe with Dean-Stark filled with SOLVESSO 100. Perform azeotropic distillation until the final viscosity at UW is reached (diluted to 50% TNV using a 10:1 diethylene glycol monobutyl ether: 2-butoxyethanol solution). Measure the viscosity according to ASTM D1545-89 ('Standard Test Method for Viscosity of Transparent Liquids by Bubble Time Method'). The resulting phosphorylated polyester material was then dissolved in components 10 and 11 to produce a resin with 50% by weight solids.

[0418] The resulting phosphorylated polyester has a glass transition temperature (Tg) of -5°C.

[0419] Table 3 – Composition of Polyester Example 4

[0420]

[0421] Comparative coating composition 1

[0422] Comparative coating composition 1 was prepared according to the formulations in Table 4. All quantities are given in grams (g) unless otherwise specified.

[0423] Examples of coating compositions 1 to 3

[0424] Prepare coating compositions 1 to 3 according to the formulations in Table 4. Unless otherwise specified, all amounts are given in grams (g).

[0425] Table 4 – Comparative Formulations of Coating Composition 1 and Coating Compositions 1 to 3

[0426]

[0427] 1 Carnauba wax dispersion, commercially available from Michelman, Inc.

[0428] 2 Hydroxymethyl type, highly reactive n-butylated benzoguanamine-formaldehyde resin, commercially available from Ineos

[0429] 3 PTFE-modified polyethylene wax is commercially available from Lubrizol Advanced Materials, Inc.

[0430] 4 Commercially available from Exxon Mobil

[0431] 5 Additives, commercially available from Dynea

[0432] Table 5 – Test Results

[0433]

[0434] *Cannot be obtained

[0435] The above results show that the coating with the glass transition temperature (Tg) according to the present invention exhibits improved venting compared to the comparative coating.

[0436] Water-based polyester examples

[0437] Polyester Example 6

[0438] An adhesive accelerator in the form of an amine-neutralized phosphorylated polyester is formed by mixing the polyester of Example 4 with dimethylethanolamine in the amounts shown below.

[0439]

[0440] Polyester Example 7

[0441] 110.14 g of 85% phosphoric acid and 89.3 g of butanol were added to a flask. The mixture was heated to 230°F (110°C) under a nitrogen inert covering. Once this temperature was reached, the nitrogen covering was turned off and a premix of 463.3 g of 1,4-cyclohexanediethanol glycidyl ether (0.286 equivalents of phosphoric acid per epoxide) and 151.27 g of butanol was fed over 2 hours and 10 minutes. The batch temperature was kept below 245°F (118°C) during the addition. After the feeding was complete, 13.7 g of butanol was added to the flask and the temperature was lowered to 219°F (104°C) and held for another 2 hours. Then 17.3 g of butanol was added to the flask, and the resulting phosphorylated polyester had 65.91% resin solids by weight.

[0442] Polyester Example 8

[0443] An adhesion promoter in the form of phosphorylated polyester neutralized with amine is formed by mixing the phosphorylated polyester of Example 7 with deionized water and dimethylethanolamine in the amounts shown below.

[0444]

[0445] Coating Composition Example 4

[0446] A water-based polyester coating composition based on Toyobo Vylonal KMD-003 (30% solids; containing polyester resin, DI H2O and 2-butoxyethanol in a ratio of 30 / 60 / 10; pH 7-9; Mn = 10,000; Tg = 53°C; OH value = 4; acid value = 14) was produced by mixing the components shown below.

[0447]

[0448] Example 5 of coating composition

[0449] A water-based polyester coating based on Toyobo Vylonal KMD-003 is produced by mixing the components shown below.

[0450]

[0451] Coating Composition Example 6

[0452] A water-based polyester coating based on Toyobo Vylonal KG-0500 (30.7% solids; containing polyester, DI H2O and 2-butoxyethanol in a ratio of 30.7 / 59.3 / 10; pH 7.4; Tg = 80°C; acid value = 16.4) was produced by mixing the components shown below.

[0453]

[0454] Table 6 – Test Results

[0455]

[0456] Examples of water-based acrylic polyester resins

[0457] Polyester Example 9

[0458] Add components 1-4 from Table 7 to a 3L round-bottom flask equipped with a nitrogen-coated atmosphere, temperature probe, Vigréux column, column temperature probe, and condenser. Heat the flask to carry out the esterification reaction and distill the water while maintaining a column temperature of 96°C and a maximum batch temperature of 230°C. Once the water distillation is complete, cool the flask to <150°C. Then add components 5 and 6 to the flask and heat it to 195°C and hold until the acid value is <25.00 mg KOH / g, on a solids basis. Then cool the flask to <150°C. Then add charge 7 to the flask and replace the Vigréux column and column temperature probe with Dean-Stark filled with SOLVESSO 100 solvent. Then heat the flask to 200°C. Maintain azeotropic reflux to remove the water formed by the esterification reaction until the final viscosity of Z4-Z5 (25°C, 45% TNV in N-methyl-2-pyrrolidone). Viscosity was measured according to ASTM D1545-89 ('Standard Test Method for Viscosity of Transparent Liquids by Bubble Time Method'). The resulting polyester material was then dissolved in component 8 to produce a composition with 70% by weight solids.

[0459] Table 7 - Composition of Polyester Example 9

[0460]

[0461] Acrylic polyester resin Example 1

[0462] Polyester Example 9 was subjected to a grafting process using the following method to graft an acrylic substance onto the unsaturated functional groups (given by maleic anhydride) of the polyester resin backbone to form acrylic polyester resin Example 1.

[0463] Half the amount of polyester Example 9 given in Table 8 was added to the container at 225 rpm and heated to 110°C. Once at 110°C, half the total amount of each acrylic monomer was added over 80 minutes with continuous stirring. 20 minutes after the addition of the acrylic monomers, 40% of each of the tert-butyl peroctanoate initiator and Dowanol DPM was added over 60 minutes. The remaining amount of polyester Example 9 was then added and the solution was heated back to 120°C. At this stage, the solution was homogeneous and well mixed. The remaining acrylic monomers were then added over 80 minutes with continuous stirring. 20 minutes after the addition of the acrylic monomers, 40% of each of the tert-butyl peroctanoate initiator and Dowanol DPM was added over 60 minutes. The remaining tert-butyl peroctanoate initiator and Dowanol DPM were then added in two uniformly separated batches. The first batch was added after 5 minutes, and the mixture was then held at 120°C for 30 minutes. The second batch was then added after 5 minutes, and the mixture was held at 120°C for 30 minutes. The reaction mixture is then cooled to below 100°C.

[0464] Table 8 - Composition of acrylic polyester resin in Example 1

[0465]

[0466] Example 1 of aqueous dispersion

[0467] An aqueous dispersion of acrylic polyester resin 1 was formed by heating the resin shown in Table 9 to 90°C and adding DMEA while stirring during heating. The mixture was then held for 10 minutes, followed by the addition of deionized water over 60 minutes, maintaining the temperature at 85°C. The aqueous dispersion was then cooled to 45°C.

[0468] Table 9 - Composition of Aqueous Dispersion Example 1

[0469]

[0470] Coating Composition Example 7

[0471] The aqueous dispersion of Example 1 was formulated into a coating composition using the components shown in Table 10.

[0472] Table 10 - Composition of Coating Composition Example 7

[0473]

[0474] Table 11 – Results

[0475]

[0476] As the results above show, the coating composition according to the invention provides excellent venting. Furthermore, the coating composition according to the invention provides a combination of excellent venting and good to excellent coating integrity.

[0477] Note all papers and documents submitted concurrently with or prior to this specification concerning this application and made publicly available with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0478] All features disclosed in this specification (including any appended claims and abstract) and / or all steps of any method or process so disclosed may be combined in any combination, except for at least some mutually exclusive combinations of such features and / or steps.

[0479] Unless otherwise expressly stated, each feature disclosed in this specification (including any appended claims and abstract) may be replaced by an alternative feature having the same, equivalent, or similar purpose. Therefore, unless otherwise expressly stated, each disclosed feature is merely an example of a general series of equivalents or similar features.

[0480] This invention is not limited to the details of one or more of the foregoing embodiments. The invention extends to any new one or any new combination of the features disclosed in this specification (including any appended claims and abstract), or to any new one or any new combination of the steps of any method or process so disclosed.

Claims

1. Use of a coating composition in reducing or preventing insufficient venting of a beverage can, the beverage can comprising a can body and a can end having a score line on the can end, wherein the coating composition comprises a polyester material, wherein the polyester material contains less than 1000 ppm of phenolic groups, wherein the coating composition is applied to at least an inner surface of the can end over at least a portion of the score line, and wherein a cured film formed from the coating composition has a glass transition temperature (Tg) of at least 50 °C, and wherein the cured film has a Young's modulus of > 0.6 GPa.

2. A method of coating a can comprising a can body and a can end having a score line on the can end, wherein the method comprises applying a coating composition to at least a portion of an inner surface of the can end over at least a portion of the score line, the coating composition comprising a polyester material, wherein the polyester material contains less than 1000 ppm of phenolic groups; and curing the coating composition to form a cured film, wherein the cured film has a glass transition temperature (Tg) of at least 50 °C, wherein the can, when filled with a carbonated beverage and sealed, exhibits sufficient venting when the score line is ruptured.

3. The use or method of claim 1 or claim 2, wherein the polyester material is obtainable by polymerising a polyacid component and a polyol component, wherein the polyacid component comprises terephthalic acid (TPA), isophthalic acid (IPA), dimethyl terephthalate, dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, adipic acid, phthalic anhydride, maleic anhydride and / or fumaric anhydride.

4. The use or method of any preceding claim, wherein the polyester material is obtainable by polymerising a polyacid component and a polyol component, wherein the polyol component comprises propylene glycol, 2-methyl propylene glycol (2-MPD), neopentyl glycol (NPG), 1,4-cyclohexane dimethanol (CHDM), butyl ethyl propylene glycol (BEPD), trimethylolpropane (TMP) and / or 1,6-hexanediol.

5. The use or method of claim 3 or claim 4, wherein the polyacid component and / or the polyol component of the polyester material comprises a Tg-boosting monomer, the Tg-boosting monomer comprising: (i) a polyacid or polyol containing an optionally substituted naphthalene group, or a hydrogenated derivative thereof; (ii) a polyacid or polyol comprising two optionally substituted 5 or 6-membered cyclic groups, wherein the cyclic groups do not share an atom, and wherein the cyclic groups are bonded directly or separated by one carbon atom; (iii) a polyacid or polyol containing an optionally substituted furan group; (iv) a polyacid or polyol containing an optionally substituted fused bicyclic group, wherein each ring is a five-membered ring and wherein one or both rings can contain a heteroatom in the ring; (v) a polyacid or polyol containing an optionally substituted bridged tricyclodecane group; ​ ​ ​ ​ ​ ​ ​ (vi) a polyacid or polyol containing an optionally substituted bridged norbornene group, or a hydrogenated derivative thereof; (vii) a polyacid or polyol containing an optionally substituted 5 or 6 membered cyclic alkyl or aromatic group; (viii) a polyacid or polyol monomer containing a branched alkyl group, wherein the monomer comprises at least one quaternary carbon atom and is formed from 5 to 10 carbon atoms, and wherein the carbon atom bonded to the acid or hydroxyl group is a primary carbon atom; (ix) a polyacid or polyol containing an optionally substituted tetraoxaspiro[5.5]undecane group; and / or (x) diols according to formula (I) wherein R1and R2each independently represent a hydrogen group, a lower alkyl group or an aryl group having 6 to 12 carbon atoms, wherein at least one of R1or R2is a lower alkyl group or an aryl group having 6 to 12 carbon atoms; and R3and R4each independently represent a lower alkyl group or an aryl group having 6 to 12 carbon atoms.

6. The use or method of any preceding claim, wherein the cured film formed from the coating composition has a glass transition temperature (Tg) of 65 to 110 °C.

7. The use or method of any preceding claim, wherein the polyester material has a Mn of 5,000 to 25,000 Da as determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11.

8. The use or method of any preceding claim, wherein the polyester material has a total hydroxyl value of 0 to 150 mgKOH / g.

9. The use or method of any preceding claim, wherein the polyester material has an acid value of 0 to 150 mgKOH / g.

10. The use or method of any preceding claim, wherein the polyester material comprises an acrylic polyester resin.

11. The use or method of claim 10, wherein the acrylic polyester resin is obtainable by grafting an acrylic polymer and a polyester material, wherein the polyester material is obtainable by polymerising: i) a polyacid component, and ii) a polyol component, wherein, one of the polyacid component or the polyol component comprises a functional monomer operable to impart a functional group onto the polyester material, such that an acrylic polymer can be grafted to the polyester material via use of the functional group.

12. The use or method of claim 11, wherein the functional monomer comprises an ethylenically unsaturated monomer operable to impart an ethylenically unsaturated functional group onto or pendant from the backbone of the polyester material.

13. The use or method of claim 12, wherein the functional monomer of the polyester material of the acrylic polyester resin comprises maleic acid, maleic anhydride and / or fumaric acid.

14. The use or method of any preceding claim, wherein the coating composition has a Young’s modulus of 0.6 to 3 gigapascals (GPa).

15. The use or method of any preceding claim, wherein the coating composition is a liquid coating composition or a powder coating composition.

16. The use or method of any preceding claim, wherein the coating composition additionally comprises a second polyester material in addition to the polyester material.

17. The use or method of any preceding claim, wherein the coating composition comprises an adhesion promoter.

18. The use or method of claim 17, wherein the adhesion promoter comprises an acidic polyester.

19. The use or method of claim 18, wherein the acidic polyester comprises a reaction product of a reaction mixture comprising: (a) a precursor polyester resin that is a condensate of: (I) a polyol component comprising a mixture of diols and triols; and (II) a polyacid component comprising a, -unsaturated polycarboxylic acid; and (b) a phosphorus-containing acid.

20. The use or method of any preceding claim, wherein the polyester material and / or coating composition is substantially free of bisphenol A (BPA) and derivatives thereof.

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