[go: up one dir, main page]

WO2025038370A1 - Composition de revêtement - Google Patents

Composition de revêtement Download PDF

Info

Publication number
WO2025038370A1
WO2025038370A1 PCT/US2024/041401 US2024041401W WO2025038370A1 WO 2025038370 A1 WO2025038370 A1 WO 2025038370A1 US 2024041401 W US2024041401 W US 2024041401W WO 2025038370 A1 WO2025038370 A1 WO 2025038370A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
coating composition
copolymer
acid
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/041401
Other languages
English (en)
Inventor
Christopher Michael HURLEY
Youssef Moussa
Wenchao Zhang
Hanzhen Bao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of WO2025038370A1 publication Critical patent/WO2025038370A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present disclosure relates to a coating composition.
  • the disclosure relates to a coating composition for food and/or beverage packaging.
  • the present disclosure extends to articles coated with the coating composition and to methods of preparing and applying the coating composition.
  • Coatings are used in a wide variety of different applications. For example, many different coatings have been used to coat food and/or beverage packaging. Coating systems typically have certain properties such as being capable of high-speed application, having acceptable adhesion to the substrate, being safe for food contact and having properties that are suitable for their end use. Typically, coatings have one, or maybe two, of these advantageous properties depending on their final end use.
  • a coating composition comprising: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a polyester-(co)polymer(B) block and/or graft copolymer film former material wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises a residue of a polymerisable material, wherein the residue comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group.
  • a package at least partially coated with a coating system that comprises a top-coat coating formed from a composition comprising: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a coated substrate comprising a coating extending over at least a part of the substrate, wherein the coating is obtainable from a coating composition comprising: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a method of coating at least a portion of a substrate comprising: a. contacting a coating composition with the substrate; b. curing the coating composition on the substrate to form a coating; wherein the coating composition comprises: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a package coated at least in part with a coating composition comprising: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a method of reducing enamel rating, solvent fraction and/or feathering comprising, a. contacting a coating composition with the substrate; b. curing the coating composition on the substrate to form a coating; wherein the coating composition comprises: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • a coating composition to reduce enamel rating, solvent fraction and/or feathering comprising: a. a film former material; and b. a residue of a polymerisable material, wherein the residue comprises a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein
  • the coating composition comprises a polyester-(co)polymer(B) block and/or graft copolymer film former material, wherein the block and/or graft copolymer comprises a polyester (co)polymer and a (co)polymer(B), wherein (co)polymer(B) comprises the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group; and/or
  • the coating composition comprises a copolymer additive, wherein the copolymer additive comprises the polymerisable material residue comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group, wherein the copolymer additive is obtainable by polymerising an ethylenically unsaturated material with the polymerisable material.
  • the present disclosure may provide a coating with improved properties, for example, improved enamel rating, adhesion, solvent fraction, and/or feathering.
  • improved properties are beneficial in applications including packaging, such as for food and beverage packaging.
  • the present disclosure may provide an internal coating for use with a food and/or beverage can, such as with an easy open can end, that has improved adhesion.
  • the present disclosure may also provide a coating having improved adhesion in combination with maintained and/or improved properties such as enamel rating, solvent fraction, blush and/or feathering.
  • feathering occurs a portion of the film will be present extending into the opening of the can. For example, this can occur with beverage cans having a pull tab or a can having a full aperture EOE. Feathering is an undesirable phenomenon from a safety perspective due to potential ingestion of the coating. As such, it is beneficial if feathering can be reduced in applications including packaging, such as for food and beverage packaging.
  • film former it is meant a compound that can form a self-supporting continuous coating film on at least a horizontal surface of a substrate.
  • the film former material may comprise a (co)polymer.
  • the film former material may comprise a film former polyester (co)polymer, a film former (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, and/or a film former polyvinyl butyral material.
  • a (co)polymer(A)-(co)polymer(B) block copolymer may be obtainable by reacting reactants comprising (co)polymer(B) material with a (co)polymer(A), wherein the (co)polymer(A) comprises a substantially terminal ethylenically unsaturated functional group, wherein the (co)polymer(B) material is reacted with the (co)polymer(A) so that the (co)polymer(B) material bonds to the (co)polymer(A) via the substantially terminal ethylenically unsaturated functional group.
  • (co)polymer(A)-(co)polymer(B) block copolymer herein it is meant a block (co)polymer comprising a (co)polymer(B) bonded to a substantially terminal end of a (co)polymer(A), such as a substantially terminal end of the backbone of (co)polymer(A).
  • the block structure may be defined as A-Z-B, wherein A is a (co)polymer(A), B is a (co)polymer(B) and Z is a residue formed from a substantially terminal ethylenically unsaturated functional group linking the (co)polymer(A) and (co)polymer(B).
  • the (co)polymer(A)-(co)polymer(B) block copolymer may also further comprise graft bonding on the backbone of the (co)polymer(A) (or a group pendent therefrom) at a part of the backbone that is not a substantially terminal end. Graft bonding on the (co)polymer(A) backbone away from a substantially terminal end may form a minority of the (co)polymer(A)-(co)polymer(B) bonds in the (co)polymer(A)-(co)polymer(B) block copolymer, such as ⁇ 30% of the bonds, or ⁇ 20%, or ⁇ 10%.
  • a majority of the (co)polymer(A)-(co)polymer(B) bonds may be in the form of (co)polymer(B) bonded to a substantially terminal end of the (co)polymer(A), such as >60% of the bonds, or >80% or >90%.
  • the (co)polymer(A)- (co)polymer(B) block copolymer may be substantially free of acrylic material graft bonds on the backbone of the (co)polymer(A) at a part of the backbone that is not a substantially terminal end, such as ⁇ 5% of the bonds, or ⁇ 3%, or ⁇ 2%.
  • substantially terminal' as used herein in relation to the hydroxyl, carboxylic acid and/or ethylenically unsaturated functional group may mean that the functional group is arranged on a monomer residue that is ⁇ 5 monomer units to a terminal monomer unit in the backbone of (co)polymer(A), or ⁇ 3 or ⁇ 2 monomer units or is adjacent a terminal monomer unit, or may be a terminal monomer unit in the backbone of (co)polymer(A).
  • a terminal monomer unit in the backbone of (co)polymer(A) as used herein may be a monomer unit of the (co)polymer(A) that is at the end of the backbone chain of (co)polymer(A).
  • a terminal monomer may comprise only one covalent bond joining the monomer to the polymer backbone.
  • a terminal monomer unit may comprise only one of the ‘bonding moieties’ of the (co)polymer backbone joining the terminal monomer with the backbone.
  • the ‘bonding moiety' of the (co)polymer(A) will depend on the (co)polymer used, e.g., for a polyester, the bonding moiety will be an ester moiety.
  • terminal may mean that the monomer comprising the hydroxy, carboxylic acid or ethylenically unsaturated functional group is bonded to the (co)polymer backbone through a single bonding moiety.
  • the (co)polymer(A) comprising a substantially terminal ethylenically unsaturated functional group may be obtainable by reacting reactants comprising a substantially terminal hydroxyl- functional group or a substantially terminal carboxylic acid-functional group of a (co)polymer(A)- precursor with a material comprising an ethylenically unsaturated group or precursor thereof to form (co)polymer(A) comprising a substantially terminal ethylenically unsaturated functional group.
  • the material may be operable to impart ethylenically unsaturated functionality to a substantially terminal end of the (co)polymer(A)-precursor.
  • the moiety formed at the bond between the (co)polymer(A)-precursor and the material comprising an ethylenically unsaturated group or precursor thereof may be a residue of a ringopening reaction between the substantially terminal hydroxyl or carboxylic acid group and the material comprising an ethylenically unsaturated group or precursor thereof.
  • the material comprising an ethylenically unsaturated group or precursor thereof may comprise a functional group having a ring that is operable to open upon reaction with the substantially terminal hydroxyl or carboxylic acid-group, such as an anhydride and/or epoxy functional group.
  • the moiety formed at the bond between the (co)polymer(A)-precursor and the material comprising an ethylenically unsaturated group or precursor thereof may be a hydroxy-ester moiety.
  • the moiety formed at the bond between the (co)polymer(A)-precursor and the material comprising an ethylenically unsaturated group or precursor thereof may be a hydroxyester moiety.
  • the carboxylic acid functional-group may be in the form of the acid, salt, anhydride, ester, or any other suitable derivative thereof.
  • suitable derivative thereof in relation to the carboxylic acid, it is meant a form of the carboxylic acid-functional group that is operable to be reacted with the material comprising an ethylenically unsaturated group or precursor thereof to form ethylenically unsaturated functionality to a substantially terminal end of the (co)polymer(A)- precursor.
  • the material comprising an ethylenically unsaturated group or precursor thereof may comprise a monomer, an oligomer and/or a (co)polymer, such as a monomer or an oligomer.
  • the material comprising an ethylenically unsaturated group or precursor thereof may comprise a monomer.
  • the material comprising an ethylenically unsaturated group or precursor thereof may comprise an anhydride, a vinyl monomer and/or an acrylic monomer.
  • precursor thereof with respect to the ethylenically unsaturated group of the material comprising an ethylenically unsaturated group or precursor thereof may mean a group that is operable to form an ethylenically unsaturated group after the material comprising an ethylenically unsaturated group precursor has been reacted with a substantially terminal hydroxylgroup or a substantially terminal carboxylic acid-group of a (co)polymer(A)-precursor, wherein the ethylenically unsaturated group may be formed from the precursor group during the reaction with the (co)polymer(A)-precursor or subsequently.
  • the substantially terminal hydroxyl-group or substantially terminal carboxylic acid-group of a (co)polymer(A)-precursor may be reacted with a material comprising an ethylenically unsaturated group.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal hydroxyl-group, may comprise carboxylic acid and/or anhydride functionality, such as a carboxylic acid and/or anhydride functional acrylic monomer.
  • the material comprising an ethylenically unsaturated group or precursor thereof may comprise: (meth)acrylic acid anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, oxalocitraconic anhydride, mesaconic anhydride, phenyl maleic anhydride, t-butyl maleic anhydride, nadic anhydride, and/or methyl maleic anhydride.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal hydroxyl-group, may comprise (meth)acrylic acid anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, and/or maleic anhydride.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal hydroxyl-group, may comprise (meth)acrylic acid anhydride, tetrahydrophthalic anhydride and/or dodecenyl succinic anhydride.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group, may comprise epoxy functionality, such as a monoepoxide.
  • the material comprising an ethylenically unsaturated group or precursor thereof, such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group may comprise an epoxy functional acrylic monomer.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group, may comprise a glycidyl ester, such as glycidyl (meth)acrylate.
  • the material comprising an ethylenically unsaturated group may comprise glycidyl methacrylate.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group, may comprise hydroxyl functionality.
  • the material comprising an ethylenically unsaturated group or precursor thereof, such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group may comprise a hydroxyl functional acrylic monomer.
  • the material comprising an ethylenically unsaturated group or precursor thereof such as for a (co)polymer(A)-(co)polymer(B) block copolymer obtainable from a (co)polymer(A)-precursor comprising a substantially terminal carboxylic acid-group, may comprise hydroxy ethyl (meth)acrylate.
  • the material comprising an ethylenically unsaturated group or precursor thereof may be present as a proportion of the total solid weight of the monomers used to form (co)polymer(A) in an amount of ⁇ 0.01 wt.%, such as ⁇ 0.5 wt%.
  • the material comprising an ethylenically unsaturated group or precursor thereof may be present as a proportion of the total solid weight of (co)polymer(A) in an amount of ⁇ 10 wt.%, such as ⁇ 5 wt%.
  • the material comprising an ethylenically unsaturated group or precursor thereof may be present as a proportion of the total solid weight of (co)polymer(A) in an amount of from 0.01 to 10 wt.%, such as from 0.5 to 5 wt%.
  • the material comprising an ethylenically unsaturated group or precursor thereof may have a molecular weight of ⁇ 750 Da, such as ⁇ 500 Da, or ⁇ 300 Da.
  • the material comprising an ethylenically unsaturated group or precursor thereof may have a molecular weight of from 50 Da to 750 Da, such as from 75 Da to 500 Da, such as from 100 Da to 300 Da.
  • molecular weight in relation to the material comprising an ethylenically unsaturated group or precursor thereof it is meant the molecular weight resulting from the sum of the atomic weights of the constituent atoms of a molecule of the material.
  • the (co)polymer(A) comprising a substantially terminal ethylenically unsaturated functional group may be obtainable by reacting reactants comprising a substantially terminal carboxylic acid or hydroxyl-functional group of a (co)polymer(A)-precursor with a material comprising an ethylenically unsaturated group or precursor thereof in the presence of a catalyst operable to promote the reaction of the material comprising an ethylenically unsaturated group or precursor thereof with the carboxylic acid or hydroxyl-functional group.
  • the catalyst such as a catalyst for use with a substantially terminal hydroxyl-functional group may comprise an amine-based catalyst, such as a tertiary amine-based catalyst.
  • the catalyst may comprise a cyclic tertiary amine-based catalyst, such as triethylenediamine.
  • the catalyst such as a catalyst for use with a substantially terminal carboxylic acidfunctional group may comprise a phosphonium-based catalyst, such as an aryl and alkyl substituted phosphonium-based catalyst, such as ethyl triphenyl phosphonium iodide.
  • a (co)polymer(A)-(co)polymer(B) graft copolymer may comprise the (co)polymer(B) grafted with the (co)copolymer(A).
  • ‘(co)polymer(A)-(co)polymer(B) graft copolymer’ herein it is meant a graft (co)polymer comprising a (co)polymer(B) bonded to the backbone of the (co)polymer(A) (or to a group pendent therefrom) at a part of the backbone that is not a substantially terminal end of the (co)polymer(A).
  • the (co)polymer(A)-(co)polymer(B) graft copolymer may also further comprise block bonding on a substantially terminal end of the (co)polymer(A).
  • Block bonding at a (co)polymer(A) substantially terminal end may form a minority of the (co)polymer(A)- (co)polymer(B) bonds in the (co)polymer(A)-(co)polymer(b) graft copolymer, such as ⁇ 30% of the bonds, or ⁇ 20%, or ⁇ 10%.
  • a majority of the (co)polymer(A)-(co)polymer(B) bonds may be in the form of (co)polymer(B) bonded to a part of the backbone that is not a substantially terminal end of the (co)polymer(A), such as >60% of the bonds, or >80% or >90%.
  • the (co)polymer(A)- (co)polymer(B) graft copolymer may be substantially free of (co)polymer(B) block bonds, such as ⁇ 5% of the bonds, or ⁇ 3%, or ⁇ 2%.
  • the (co)polymer(A)/(co)polymer(A)-precursor may be a polyester (co)polymer, a polyurethane (co)polymer; a polyolefin (co)polymer, such as polybutadiene; and/or an epoxy (co)polymer, such as an epoxy (co)polymer that is substantially free of bisphenol A (BPA), bisphenol F (BPF), bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), and derivatives thereof.
  • BPA bisphenol A
  • BPF bisphenol F
  • BADGE bisphenol A diglycidyl ether
  • BFDGE bisphenol F diglycidyl ether
  • Substantially free in relation to the epoxy (co)polymer refers to epoxy (co)polymers containing less than 1000 parts per million (ppm) of any of the compounds or derivatives thereof mentioned above. “Essentially free” refers to epoxy (co)polymers containing less than 100 ppm of any of the compounds or derivatives thereof mentioned above. By “completely free” refers to epoxy (co)polymers containing less than 20 parts per billion (ppb) of any of the compounds or derivatives thereof mentioned above.
  • the (co)polymer(A)/(co)polymer(A)-precursor may be a polyester (co)polymer.
  • the (co)polymer(A)-(co)polymer(B) block and/or graft copolymer may comprise a polyester- (co)polymer(B) block and/or graft copolymer.
  • the polyester (co)polymer may comprise a linear polyester.
  • the polyester (co)polymer may comprise a saturated polyester (co)polymer.
  • the polyester (co)polymer may be obtainable by ring opening polymerization, such as ring opening polymerization of a lactone component and/or an epoxy component.
  • the polyester (co)polymer may be obtainable by polymerizing reactants comprising:
  • the polyester (co)polymer of the polyester-(co)polymer(B) graft copolymer may be obtainable by polymerizing reactants comprising: i) a polyacid component, with
  • the polyester-(co)polymer(B) graft copolymer may be obtainable by reacting reactants comprising (co)polymer(B) material with the functional polyester (co)polymer to form a (co)polymer(B) grafted onto the polyester (co)polymer via the said functionality of the polyester (co)polymer. This grafting may occur via free radical polymerization, such as by free radical polymerization onto ethylenic unsaturation on the polyester (co)polymer.
  • Polyacid and like terms as used herein, refers to a compound having two or more carboxylic acid groups, such as two (diacids), three (triacids) or four acid groups, and includes an ester of the polyacid (wherein an acid group is esterified) or an anhydride.
  • the polyacid may be an organic polyacid.
  • the carboxylic acid groups of the polyacid may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; or an arylene group.
  • the polyester (co)polymer may be formed from any suitable polyacid.
  • suitable polyacids include, but are not limited to the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanoic diacid; dodecanoic diacid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorendic anhydride; 1 ,3-cyclohexane dicarboxylic acid; 1
  • the polyacid component may comprise a diacid.
  • diacids include, but are not limited to the following: phthalic acid; isophthalic acid; terephthalic acid; 1 ,4 cyclohexane dicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6- naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic acid; hexahydrophthalic acid; maleic acid; succinic acid; itaconic acid; di-ester materials, such as dimethyl ester derivatives for example dimethyl isophthalate, dimethyl terephthalate, dimethyl 1 ,4- cyclohexane dicarboxylate, dimethyl 2,6-naphthalene di carboxylate, dimethyl fumarate, dimethyl orthophthalate, dimethylsuccinate, dimethyl glutarate, dimethyl a
  • the polyacid component may comprise: terephthalic acid (TPA), dimethyl terephthalate, isophthalic acid (IPA), dimethyl isophthalic acid, 1 ,4 cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, 2,6- naphthalene dicarboxylic acid, phthalic anhydride, maleic anhydride, fumaric anhydride; and/or a monomer having an aliphatic group containing at least 15 carbon atoms.
  • the polyacid component may comprise: terephthalic acid, isophthalic acid, dimethyl terephthalate, hexahydrophthalic anhydride, cyclohexane 1 ,4-dicarboxylic acid, maleic anhydride, and/or a monomer having an aliphatic group containing at least 15 carbon atoms.
  • the polyol component comprises a polyol.
  • Polyol and like terms, as used herein, refers to a compound having two or more hydroxyl groups, such as two (diols), three (triols) or four hydroxyl groups (tetrols).
  • the hydroxyl groups of the polyol may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; or an arylene group.
  • the polyol may be an organic polyol.
  • the polyester (co)polymer may be formed from any suitable polyol.
  • suitable polyols include, but are not limited to the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propanediols including 1,2-propanediol; 1 ,3-propanediol; butyl ethyl propanediol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; butanediols including 1 ,4-butanediol; 1 ,3-butanediol; and 2-ethyl-1,
  • the diols may be selected from: ethylene glycol; 1,2-propane diol; 1 ,3-propane diol; 1,2- butandiol; 1 ,3-butandiol; 1 ,4-butandiol; but-2-ene 1 ,4-diol; 2,3-butane diol; 2-methyl 1 ,3-propane diol; 2,2’-dimethyl 1 ,3-propanediol (neopentyl glycol); 1 ,5 pentane diol; 3-methyl 1 ,5-pentanediol;
  • TACD 2,2,4,4-tetraalkylcyclobutane-1 ,3-diol
  • TMPD 2-trimethyl-1 ,3-pentanediol
  • diethylene glycol triethylene glycol
  • dipropylene glycol tripropylene glycol
  • 1 ,4 cyclohexane dimethanol tricyclodecane dimethanol
  • isosorbide butanediol, 1 ,4-cyclohexane diol; and/or 1 , T-isopropylidene-bis (4-cyclohexanol); and mixtures thereof.
  • the polyol component may comprise a polyol having at least three hydroxyl groups, such as trimethylol propane; pentaerythritol; di-pentaerythritol; trimethylol ethane; trimethylol butane; and/or bio-derived polyols such as glycerol and/or sorbitol.
  • the polyol component having at least three hydroxyl groups may comprise a triol or tetrol, such as trimethylol propane; pentaerythritol; trimethylol ethane; trimethylol butane and/or glycerol.
  • the polyol component having at least three hydroxyl groups may comprise a triol, such as trimethylol propane; trimethylol ethane; and/or trimethylol butane, for example trimethylol propane.
  • the polyol having at least three hydroxyl groups may be present as a proportion of the solid weight of the polyol component in an amount of >0.1wt%, such as sQ.5wt% or >0.7wt%, for example >0.8wt% or >0.9wt%, such as >1wt%.
  • the polyol having at least three hydroxyl groups may be present as a proportion of the solid weight of the polyol component in an amount of ⁇ 10wt%, such as ⁇ 8wt% or ⁇ 6wt%, for example ⁇ 5wt% or ⁇ 4wt%, such as ⁇ 3wt% or ⁇ 2wt%.
  • the polyol having at least three hydroxyl groups may be present as a proportion of the solid weight of the polyol component in an amount of from 0.1 to 10wt%, such as from 0.5 to 8wt% or from 0.7 to 6wt%, for example from 0.8 to 5wt% or from 0.9 to 4wt%, such as from 1 to 3wt% or from 1 to 2wt%.
  • the polyol component may comprise ethylene glycol (EG), 1,2-propylene glycol (PG), 2- methyl propanediol (2-MPD), neopentyl glycol (NPG), 1 ,4-cyclohexane dimethanol (CHDM), butyl ethyl propane diol (BEPD), trimethylolpropane (TMP), tricyclodecane dimethanol, butanediol and/or 1 ,6 hexanediol.
  • EG ethylene glycol
  • PG 1,2-propylene glycol
  • 2-MPD 2- methyl propanediol
  • NPG neopentyl glycol
  • CHDM 1 ,4-cyclohexane dimethanol
  • BEPD butyl ethyl propane diol
  • TMP trimethylolpropane
  • tricyclodecane dimethanol butanediol and/or 1 ,6 hexanediol.
  • the polyacid component and/or the polyol component may comprise a Tg enhancing monomer comprising:
  • each ring is a five membered ring and in which one or both rings may comprise a heteroatom in the ring;
  • a branched alkyl group-containing polyacid or polyol monomer wherein the monomer comprises at least one quaternary carbon atom and is formed of from 5 to 10 carbon atoms, and wherein the carbon atoms bonded to the acid or hydroxyl groups are primary carbon atoms;
  • (x) an aliphatic polyacid or polyol monomer wherein the monomer comprises a tetracyclic hydrocarbon ring structure.
  • the polyacid component and/or the polyol component of the polyester (co)polymer of the polyester-(co)polymer(B) graft copolymer comprises a functional monomer operable to impart functionality to the polyester (co)polymer.
  • the functionality is such that a (co)polymer(B) grafted onto the polyester (co)polymer can be formed via the use of said functionality.
  • the functionality may comprise ethylenic unsaturation, carboxylic acid functionality or epoxy functionality.
  • the functionality may be in the backbone of the polyester resin or pendant therefrom.
  • the functional monomer may comprise an ethylenically unsaturated monomer, which ethylenically unsaturated monomer may be operable to impart ethylenically unsaturated functionality on the backbone of the polyester (co)polymer, or pendant therefrom.
  • the functionality may comprise ethylenic unsaturation, which may be in the backbone of the polyester (co)polymer.
  • Suitable functional monomers comprise: maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, mesaconic acid, mesaconic anhydride, phenyl maleic acid, phenyl maleic anhydride, t-butyl maleic acid, t-butyl maleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methyl maleic acid, methyl maleic anhydride, and/or trimethylolpropane monoallyl ether.
  • the functional monomer comprises a polyacid
  • the functional monomer may be present as a proportion of the solid weight of the polyacid component in an amount of from 0.5 to 10wt%, such as from 1 to 5wt%.
  • the functional monomer comprises a polyol
  • the functional monomer may be present as a proportion of the solid weight of the polyol component in an amount of from 0.5 to 10wt%, such as from 1 to 5wt%.
  • the functional monomer of the polyester (co)polymer may comprise maleic acid, maleic anhydride and/or fumaric acid.
  • the (co)polymer(B) material may comprise (co)polymer(B) and/or monomers operable to polymerize to form (co)polymer(B).
  • the (co)polymer(B) material may comprise ethylenically unsaturated material, such as a monomer and/or a (co)polymer.
  • the ethylenically unsaturated material may comprise acrylic material, such as an acrylic monomer and/or an acrylic (co)polymer, such as an acrylic monomer.
  • the (co)polymer(B) may be an acrylic (co)polymer.
  • the (co)polymer(A)- (co)polymer(B) block and/or graft copolymer may comprise a polyester-acrylic block and/or graft copolymer.
  • the (co)polymer(B) material may be an acrylic material comprising an acrylic (co)polymer and/or monomers operable to polymerize to form an acrylic (co)polymer.
  • the acrylic monomer may comprise a (hetero)aliphatic (alk)acrylate or (alk)acrylic acid.
  • Suitable (hetero)aliphatic (alk)acrylate or (alk)acrylic acid monomers include, but are not limited to, the following: alkyl (alk)acrylate, such as Ci to Ce alkyl (Ci to Ce alk)acrylate, for example, Ci to Ce alkyl (meth)acrylate, and (alk)acrylic acid, such as (Ci to Ce alk)acrylic acid.
  • the acrylic monomers may comprise a functional group.
  • the acrylic monomer may be selected from monomers comprising methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, cyclohexyl (meth) acrylate; allyl (meth)acrylate; isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, (meth)acrylic acid, dimethylamino ethyl methacrylate, butylamino ethyl (meth)acrylate, and/or HEMA phosphate (such as ethylene glycol methacrylate phosphate).
  • monomers comprising methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, cyclohexyl (meth) acrylate; allyl (meth)acrylate; isobornyl (meth)acrylate, hydroxyethyl (me
  • alk)acrykate As used herein are used conventionally and herein to refer to both alkacrylate and acrylate, such as methacrylate and acrylate.
  • the acrylic (co)polymer/acrylic material may be formed from monomers comprising: methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, cyclohexyl (meth)acrylate, allyl (meth)acrylate, dimethylamino ethyl methacrylate, butylamino ethyl (meth)acrylate, and/or HEMA phosphate (such as ethylene glycol methacrylate phosphate).
  • monomers comprising: methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, cyclohexyl (meth)acrylate, allyl (meth)acrylate, dimethylamino ethyl methacrylate, butylamin
  • the acrylic monomers may comprise a ratio of methacrylate monomers to acrylate monomers of at least 1 :1 , such as at least 2:1 or at least 3:1 or at least 4:1, such as at least 5:1.
  • the acrylic monomers may be substantially free of acrylate monomers.
  • methacrylate monomers” and “acrylate monomers” with regard to the ratio of these types of monomers in the acrylic monomers of the acrylic (co)polymer it is meant the total number of methacrylate monomers compared to the total number of acrylate monomers across all the types of acrylic monomer that form the acrylic (co)polymer.
  • the acrylic (co)polymer is formed of methyl methacrylate, methyl acrylate and butyl acrylate, then the amount of methyl methacrylate compared to the combined amount of methyl acrylate and butyl acrylate would be at least 5:1 .
  • the acrylic monomers may comprise a hydroxyl functional monomer, such as hydroxyethyl (meth)acrylate.
  • the hydroxyl functional monomer may be present by solid weight of the acrylic (co)polymer in an amount of from 5 to 40wt%, such as from 5 to 30wt% or from 10 to 20wt%.
  • the acrylic (co)polymer/acrylic material may also comprise an amount (such as 0 to 30wt%, by solid weight of the acrylic (co)polymer) of non-acrylic monomers.
  • non acrylic monomers may include other ethylenically unsaturated monomers, such as styrene, ethylene, propylene, vinyl toluene, butadiene, 1 -octene or isoprene, vinyl esters such as vinyl acetate, and/or nitriles such as (meth)acrylonitrile.
  • the polyester-acrylic block and/or graft copolymer may be formed from the polyester (co)polymer and the acrylic (co)polymer in a weight ratio of from 99wt% to 50wt% polyester (co)polymer to from 50wt% to 1wt% acrylic (co)polymer, such as a weight ratio of from 95wt% to 60wt% polyester (co)polymer to from 40wt% to 5wt% acrylic (co)polymer, such as a weight ratio of from 90wt% to 65wt% polyester (co)polymer to from 35wt% to 10wt% acrylic (co)polymer.
  • the polyester-acrylic block and/or graft copolymer may be formed from the polyester (co)polymer and the acrylic (co)polymer in a weight ratio of 85wt% polyester (co)polymer to 15wt% acrylic (co)polymer.
  • the (co)polymer(B) may comprise the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group.
  • the term ‘residue’ with respect to monomer residue such as the residue of the polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group may mean the moiety formed by polymerisation of the polymerisable material.
  • the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group may be formed from a polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • ‘precursor thereof’ with respect to the sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group of the polymerisable material may mean a group that is operable to form a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group during the reaction with the (co)polymer(A) or subsequently.
  • the group that is operable to form a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group may comprise a sulfur- and/or phosphorus- containing group, such as a sulfur oxide- and/or phosphorus oxide- containing group.
  • the polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof may comprise a monomer and/or a (co)polymer that comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the (co)polymer(B) material may comprise the polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof, such as a monomer and/or a (co)polymer that comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the film former (co)polymer(A)-(co)polymer(B) block and/or graft copolymer may be formed by polymerizing (co)polymer(B) material comprising a polymerisable monomer that comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof in the presence of (co)polymer(A) to form the film former (co)polymer(A)- (co)polymer(B) block and/or graft copolymer.
  • the polymerisable monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof may comprise a vinyl monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the monomer may comprise vinylsulfonic acid, a vinylsulfate, vinylphosphonic acid and/or a vinylphosphate.
  • the monomer may comprise a styrene and/or ally monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof, for example styrene phosphonic acid and/or allyl phosphonic acid.
  • the monomer may comprise an acrylic monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof, for example acrylic phosphate and/or 2- sulfoethylmethacryloate.
  • the (co)polymer(B) comprising the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group may be obtainable by polymerising an ethylenically unsaturated material, such as an acrylic material, with a polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the film former (co)polymer(A)-(co)polymer(B) block and/or graft copolymer may be obtainable by polymerizing an ethylenically unsaturated material, such as an acrylic material, with a polymerizable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof in the presence of the (co)polymer(A) to form the (co)polymer(A)-(co)polymer(B) block and/or graft copolymer.
  • an ethylenically unsaturated material such as an acrylic material
  • a polymerizable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof in the presence of the (co)polymer(A) to form the (co)polymer(A)
  • the (co)polymer(B) may be formed from >0.1 % of a monomer comprising a sulfonic acid- , a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (co)polymer(B) is formed, such as >0.3 wt% or >0.5 wt%.
  • the (co)polymer(B) may be formed from ⁇ 90% of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (co)polymer(B) is formed, such as ⁇ 60 wt% or ⁇ 40 wt%.
  • the (co)polymer(B) may be formed from 0.1 to 90 % of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (co)polymer(B) is formed, such as from 0.3 to 60 wt% or from 0.5 to 40 wt%.
  • the (co)polymer(B) may be formed from ⁇ 20% of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (co)polymer(B) is formed, such as 215 wt% or 210 wt% or ⁇ 9 wt%.
  • the (co)polymer(B) may be formed from 0.1 to 20 % of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (co)polymer(B) is formed, such as from 0.3 to 15 wt% or from 0.5 to 10 wt% or from 0.5 to 9 wt%.
  • the (co)polymer(B) may be formed from >50 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which (co)polymer(B) is formed, such as S60 wt% or >70 wt% or s75 wt%.
  • the (co)polymer(B) may be formed from ⁇ 99.9 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which the (co)polymer(B) is formed, such as 299.7 wt% or ⁇ 99.5 wt%.
  • the (co)polymer(B) may be formed from 50 to 99.9 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which the (co)polymer(B) is formed, such as from 60 to 99.7. wt% or from 70 to 99.5 wt% or from 75 to 99.5 wt%.
  • the (co)polymer(B) may be formed from ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group and a material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof in a weight ratio of from 99.9 wt% to 50 wt% ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group to from 50 wt% to 0.1 wt% material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the (
  • the (co)polymer(B) may comprise hydroxyl functionality, such as by using a hydroxyl functional monomer.
  • the (co)polymer(B) may be formed from >5 % of a hydroxyl functional monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as ⁇ 8 wt% or ⁇ 10 wt%.
  • the (co)polymer(B) may be formed from ⁇ 40 % of a hydroxyl functional monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as >30 wt% or >20 wt%.
  • the (co)polymer(B) may be formed from ⁇ 9 % of an acid functional monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as >5 wt% or >1 wt% or >0.5wt%.
  • the (co)polymer(B) may be formed from >50 % of an acrylic monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as 2:70 wt% or 2:75 wt% or 2:80 wt% or >90 wt%.
  • the (co)polymer(B) may be formed from ⁇ 99% of an acrylic monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as ⁇ 98 wt% or ⁇ 95 wt%.
  • the (co)polymer(B) may be formed from 50 to 99 % of an acrylic monomer by total weight of the monomers from which the (co)polymer(B) is formed, such as from 70 to 98 wt% or from 80 to 95 wt% or from 90 to 95 wt%.
  • the ethy lenically unsaturated material may comprise ⁇ 20% of a cyclic vinyl material, such as an aromatic cyclic material, for example styrene, by total weight of the monomers from which the (co)polymer(B) is formed, such as ⁇ 10 wt% or ⁇ 5 wt% or ⁇ 1 %.
  • the ethy I en ically unsaturated material may be substantially free of cyclic vinyl material, such as an aromatic cyclic material, for example styrene.
  • the (co)polymer(B) may have a number average molecular weight (Mn) of >1 ,000 Da, such as 2:2,000 Da or >3,000 Da or >3,100 Da.
  • the (co)polymer(B) may have a number average molecular weight of ⁇ 10,000 Da, such as ⁇ 5,000 Da or ⁇ 4,900 Da, or ⁇ 4,500 Da.
  • the (co)polymer(B) may have any suitable gross hydroxyl value (OHV).
  • the (co)polymer(B) may have a gross OHV of >0 mg KOH/g, such as 2:10 mg KOH/g.
  • the (co)polymer(B) may have a gross OHV of ⁇ 410 mg KOH/g, such as of ⁇ 200 mg KOH/g.
  • the (co)polymer(B) may have a gross OHV of from >0 to 410 mg KOH/g, such as from 10 to 200 mg KOH/g.
  • the residue of a polymerisable material wherein the residue comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group / (co)polymer(B) may be prepared in the presence of a polymerisation initiator.
  • the polymerisation initiator may comprise an organic peroxide, such as a dialkyl peroxide and/or a peroxy ester, for example di-(tert-amyl) peroxide and/or tert-butyl peroctoate.
  • the polymerisation initiator may comprise a dialkyl peroxide.
  • the polyester (co)polymer may be prepared in the presence of an esterification catalyst.
  • the esterification catalyst may be chosen to promote the reaction of components by esterification and/or trans-esterification.
  • Suitable examples of esterification catalysts for use in the preparation of a polyester (co)polymer include, but are not limited to the following: metal compounds such as stannous octoate; stannous chloride; butyl stannoic acid (hydroxy butyl tin oxide); monobutyl tin tris (2-ethylhexanoate); chloro butyl tin dihydroxide; dibutyl tin oxide; tetra-n-propyl titanate; tetra- n-butyl titanate; zinc acetate; acid compounds such as phosphoric acid; para-toluene sulphonic acid; dodecyl benzene sulphonic acid (DDBSA), tetra alkyl zirconium materials, antimony
  • the esterification catalyst when present, may be used in amounts from 0.001 to 1% by weight of the total polymer components, such as from 0.01 to 0.2%, such as from 0.025 to 0.2% by weight of the total polymer components.
  • the film former material may have any suitable number-average molecular weight (Mn).
  • the film former material may have a Mn of ⁇ 35,000 Da, such as ⁇ 30,000 Da, such as ⁇ 25,000 Da, or even ⁇ 22,000 Da.
  • the film former material may have an Mn from 1 ,000 Da to 35,000 Da, such as from 2,000 Da to 30,000 Da, such as from 3,000 Da to 25,000 Da, or from 4,000 to 22,000 Da or from 8,000 to 22,000 or even from 9,000 to 22,000.
  • the film former material/(co)polymer(A)-(co)polymer(B) block and/or graft copolymer/polyester-(co)polymer(B) block and/or graft copolymer/polyvinyl butyral material, or a coating (/cured film) formed from the coating composition may have any suitable glass transition temperature (Tg).
  • the film former material/(co)polymer(A)-(co)polymer(B) block and/or graft copolymer/polyester-(co)polymer(B) block and/or graft copolymer/polyvinyl butyral material, or a coating formed from the coating composition may have a Tg of >25°C and/or ⁇ 200°C.
  • the film former material/(co)polymer(A)-(co)polymer(B) block and/or graft copolymer/polyester- (co)polymer(B) block and/or graft copolymer/polyvinyl butyral material, or a coating formed from the coating composition may have a Tg of >25°, or >30°C, or >35°C, such as >40°C or >45°C, or S5O°C, such as >55°C or >60°C.
  • the film former material/(co)polymer(A)-(co)polymer(B) block and/or graft copolymer/polyester-(co)polymer(B) block and/or graft copolymer/polyvinyl butyral material, or a coating formed from the coating composition have a Tg of ⁇ 200°C. such as ⁇ 150°C, or ⁇ 120°C, or ⁇ 1 10°C.
  • the film former material/(co)polymer(A)-(co)polymer(B) block and/or graft copolymer/polyester-(co)polymer(B) block and/or graft copolymer/polyvinyl butyral material, or a coating formed from the coating composition may have a Tg of from 25°C to 200°C, such as from 40°C to 150°C, such as from 50°C to 120°C, or from 50°C to 1 10°C, such as from 60°C to 1 10°C.
  • Tg was measured according to ASTM D6604-00(2013) (“Standard Practice for Glass Transition Temperatures of Hydrocarbon Resins by Differential Scanning Calorimetry”. Heat-flux differential scanning calorimetry (DSC), sample pans: aluminium, reference: blank, calibration: indium and mercury, sample weight: 10mg, heating rate: 20°C/min).
  • the film former material may have any suitable gross hydroxyl value (OHV).
  • the film former material may have a gross OHV from 0 to 120 mg KOH/g, such as from 0 to 70 KOH/g, or from 0 to 40 KOH/g, or from 0 to 20 KOH/g or from 0 to 15 KOH/g.
  • the hydroxyl value is the number of mg of KOH equivalent to the hydroxyl groups in 1 g of material.
  • a sample of solid polyester (0.13g) was weighed accurately into a conical flask and dissolved, using light heating and stirring as appropriate, in 20ml of tetrahydrofuran. 10ml of 0.1 M 4-(dimethylamino)pyridine in tetrahydrofuran (catalyst solution) and 5ml of a 9 vol% solution of acetic anhydride in tetrahydrofuran (i.e. 90ml acetic anhydride in 910ml tetrahydrofuran; acetylating solution) were then added to the mixture.
  • Hydroxyl value (V2 - Vi) x molarity of KOH solution (M) x 56.1 weight of solid sample (g) wherein Vi is the titre of KOH solution (ml) of the polyester sample and V2 is the titre of KOH solution (ml) of the blank sample. All values for gross hydroxyl value reported herein were measured in this way.
  • the film former material may have any suitable acid value (AV).
  • the film former material may have an AV of S3 KOH/g, such as >6 KOH/g, or >9 KOH/g.
  • the film former material may have an AV of 250 KOH/g, such as 240 KOH/g, or 230 KOH/g, or 225 KOH/g.
  • the film former material may have an AV of from 0 to 50 KOH/g, such as from 3 to 40 KOH/g, or from 6 to 30 KOH/g, or from 9 to 25 KOH/g.
  • the film former material may have an AV of 220 KOH/g, such as 210 KOH/g, or 25 KOH/g.
  • the AV was determined by titration with 0.1 M methanolic potassium hydroxide (KOH) solution.
  • KOH methanolic potassium hydroxide
  • a sample of solid polyester (0.1g) was weighed accurately into a conical flask and dissolved, using light heating and stirring as appropriate, in 25ml of dimethyl formamide containing phenolphthalein indicator. The solution was then cooled to room temperature and titrated with the 0.1 M methanolic potassium hydroxide solution.
  • the resulting acid number is expressed in units of mg KOH/g and is calculated using the following equation:
  • Acid number titre of KOH solution (ml) x molarity KOH solution (M) x 56.1 weight of solid sample (g)
  • the film former polyvinyl butyral material may be produced by any suitable method.
  • Such (co)polymer may be produced by reacting a polyvinyl alcohol with butyraldehyde.
  • Polyvinyl alcohols may be produced by the polymerisation of vinyl acetate monomer and the subsequent, alkaline-catalysed methanolysis of the polyvinyl acetate obtained.
  • the acetalisation reaction of polyvinyl alcohol and butyraldehyde is not quantitative, so the resulting polyvinyl butyral may contain a certain amount of hydroxyl groups. In addition, a small amount of acetyl groups may remain in the polymer chain.
  • the film former polyvinyl butyral material may comprise: a) a first polyvinyl butyral (co)polymer, and b) a second polyvinyl butyral (co)polymer having a higher weight-average molecular weight (Mw) than the first polyvinyl butyral (co)polymer.
  • the Mw of the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may be from 5,000 Da, such as from 10,000 Da.
  • the Mw of the polyvinyl butyral material/the second polyvinyl butyral (co)polymer may be from 20,000 Da, such as from 25,000 Da.
  • the Mw of the polyvinyl butyral material/the first and/or second polyvinyl butyral (co)polymer may be up to 75,000 Da.
  • the Mw of the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may be up to 25,000 Da, such as up to 20,000 Da.
  • the Mw of the polyvinyl butyral material/the first and/or second polyvinyl butyral (co)polymer may be from 5,000 to 75,000 Da.
  • the Mw of the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may be from 5,000 to 25,000 Da, such as from 10,000 to 20,000 Da, and/or the Mw of the polyvinyl butyral material/the second polyvinyl butyral (co)polymer may be from 20,000 to 75,000, such as from 25,000 to 75,000.
  • the coating composition may comprise any suitable polyvinyl butyral material.
  • the coating composition may comprise commercially available polyvinyl butyral (co)polymer.
  • Suitable commercially available polyvinyl butyral (co)polymer include, but are not limited to the following: the MOWITAL (registered trademark) and PIOLOFORM (registered trademark) lines of polyvinyl butyral resins commercially available from Kuraray America, Inc., New York, New York; the BUTVAR (registered trademark) line of polyvinyl butyral resins commercially available from Solutia Inc.; the S-LEC B line of polyvinyl butyral resins commercially available from Sekisui Chemical Co. LTD; and combinations thereof.
  • the first polyvinyl butyral (co)polymer may comprise MOWITAL (registered trademark) B 16 H or MOWITAL (registered trademark) B 16 S which are commercially available from Kuraray America, Inc., New York, New York.
  • the first polyvinyl butyral (co)polymer may comprise MOWITAL (registered trademark) B 16 S.
  • the second polyvinyl butyral (co)polymer may comprise MOWITAL (registered trademark) B 30 HH which is commercially available from Kuraray America, Inc., New York, New York.
  • the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may have any suitable weight-average molecular weight (Mw).
  • Mw weight-average molecular weight
  • polyvinyl butyral material/the first polyvinyl butyral (co)polymer may have a Mw of from 12,000 to 18,000 Da, or even from 15,000 to 17,000 Da.
  • the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may have an Mw of at least 12,000 Da, such as at least 15,000 Da.
  • the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may have an Mw of up 18,000 Da, such as up to 17,000 Da.
  • the polyvinyl butyral material/the first polyvinyl butyral (co)polymer may have an Mw of from 12,000 Da to 20,000 Da, such as from 15,000 Da to 20,000 Da.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have an Mw from 10,000 Da to 18,000 Da, such as from 12,000 Da to 18,000 Da, such as from 15,000 Da to 18,000 Da.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a Mw of from 10,000 Da to 17,000 Da, such as from 12,000 Da to 17,000 Da, such as from 15,000 Da to 17,000 Da.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have any suitable degree of butyration, which may be defined as the proportion of hydroxyl groups which are reacted with the butyraldehyde.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a degree of butyration from 10 to 100 mol%, such as from 30 to 100 mol%, such as from 40 to 95 mol%, or even from 50 to 95 mol%.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a degree of butyration from 70 to 95 mol%.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a degree of butyration from 78 to 85 mol%.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have any suitable residual hydroxyl groups (OH) content from the polyvinyl alcohol.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a residual OH content from 1 to 20 mol% such as from 5 to 20 mol%, or even from 10 to 20 mol%.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have an OH content of from 1 to 18 mol%.
  • residual hydroxyl group refers to unreacted hydroxyl groups.
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have any suitable glass transition temperature (Tg).
  • the polyvinyl butyral material /the first polyvinyl butyral (co)polymer may have a Tg from 40 to 100 °C, such as from 50 to 90 °C, such as from 55 to 70 °C.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have any suitable weight-average molecular weight (Mw).
  • polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw from 26,000 to 50,000 Da, such as from 28,000 to 40,000 Da, or even from 29,000 to 35,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw from 25,000 to 35,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw of at least 26,000 Da, such as at least 28,000 Da, or even at least 29,000 Daltons.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw of up to 50,000 Da, such as up to 35,000 Da, or even up to 31 ,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw from 26,000 Da to 75,000 Da, such as from 28,000 Da to 75,000 Da, or even from 29,000 Da to 75,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw from 25,000 Da to 50,000 Da, such as from 26,000 Da to 50,000Da, such as from 28,000 Da to 50,000 Da, or even from 29,000 Da to 50,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have an Mw from 25,000 Da to 40,000 Da, such as from 26,000 Da to 40,000 Da, such as from 28,000 Da to 40,000 Da, or even from 29,000 Da to 40,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Mw from 25,000 Da to 35,000 Da, such as from 26,000 Da to 35,000 Da, such as from 28,000 Da to 35,000 Da, or even from 29,000 Da to 35,000 Da.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have any suitable degree of butyration, which may be defined as the proportion of hydroxyl groups which are reacted with the butyraldehyde.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a degree of butyration from 10 to 100 mol%, such as from 30 to 100 mol%, such as from 40 to 95 mol%, or even from 50 to 95 mol%.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a degree of butyration from 75 to 95 mol%.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a degree of butyration from 82 to 88 mol%.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have any suitable residual hydroxyl group (OH) content.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a residual OH content from 10 to 50 mol%, such as from 10 to 40 mol%, or even from 15 to 30 mol%.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have an OH content of 10 to 15 mol%.
  • residual hydroxyl groups refers to unreacted hydroxyl groups.
  • the second polyvinyl butyral (co)polymer may have a lower hydroxyl (OH) content than the first polyvinyl butyral (co)polymer.
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have any suitable glass transition temperature (Tg).
  • Tg glass transition temperature
  • the polyvinyl butyral material /the second polyvinyl butyral (co)polymer may have a Tg from 40 to 90 °C, such as from 50 to 80 °C, or even from 60 to 70 °C.
  • the film former polyvinyl butyral material may comprise any suitable weight ratio of the first and second polyvinyl butyral (co)polymers.
  • the weight ratio of first and second polyvinyl butyral (co)polymers may be from 10:1 to 1 :10, such as from 7:1 to 1 :7, such as from 5:1 to 1 :5, or even from 2:1 to 1 :2.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be 1 :1.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be at least 10:1, such as at least 7:1 , such as 5:1 or even 2:1.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be up to 1 :10, such as up to 1 :7, such as up to 1 :5, or even up to 1 :2.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be from 10:1 to 1 :10, such as from 7:1 to 1 :10, such as from 5:1 to 1 :10, or even from 2:1 to 1 :10.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be from 10:1 to 1 :7, such as from 7:1 to 1 :7, such as from 5:1 to 1 :7, or even from 2:1 to 1 :7.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be from 10:1 to 1 :5, such as from 7:1 to 1 :5, such as from 5:1 to 1 :5, or even from 2:1 to 1 :5.
  • the weight ratio of the first:second polyvinyl butyral (co)polymers may be from 10:1 to 1 :2, such as from 7:1 to 1 :2, such as from 5:1 to 1 :2, or even from 2:1 to 1 :2.
  • the coating composition may comprise a copolymer additive, wherein the copolymer additive comprises the residue of a polymerisable material comprising a sulfonic acid-, a sulfate- , a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the polymerisable material may comprise a polymerisable monomer and/or a (co)polymer that comprises a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the polymerisable monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof may comprise a vinyl monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the monomer may comprise vinylsulfonic acid, a vinylsulfate, vinylphosphonic acid and/or a vinylphosphate.
  • the monomer may comprise a styrene and/or ally monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof, for example styrene phosphonic acid and/or allyl phosphonic acid.
  • the monomer may comprise an acrylic monomer having a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof, for example acrylic phosphate and/or 2- sulfoethylmethacryloate.
  • the copolymer additive comprising the polymerisable material residue comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group may be obtainable by polymerising an ethylenically unsaturated material with a polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof.
  • the said ethylenically unsaturated material that may be polymerised with the polymerisable material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group.
  • the ethylenically unsaturated material of the copolymer additive may comprise a monomer and/or a (co)polymer.
  • the ethylenically unsaturated material may comprise acrylic material, such as an acrylic monomer and/or an acrylic (co)polymer, such as an acrylic monomer.
  • the acrylic monomer may comprise a (hetero)aliphatic (alk)acrylate or (alk)acrylic acid.
  • Suitable (hetero)aliphatic (alk)acrylate or (alk)acrylic acid monomers include, but are not limited to, the following: alkyl (alk)acrylate, such as Ci to Ce alkyl (Ci to Ce alk)acrylate, for example, Ci to Ce alkyl (meth)acrylate, and (alk)acrylic acid, such as (Ci to Ce alk)acrylic acid.
  • the acrylic monomers may comprise a functional group.
  • the acrylic monomer may be selected from (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate; propyl (meth)acrylate; butyl (meth)acrylate; cyclohexyl (meth)acrylate; benzyl methacrylate; 2-ethylhexyl (meth)acrylate; isobornyl (meth)acrylate; lauryl (meth)acrylate; hydroxyl-functional acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, amine-functional acrylates such as dimethylamino ethyl methacrylate, butylamino ethyl (meth)acrylate, and/or glycidyl-functional acrylates such as glycidyl (meth)acrylate.
  • the acrylic monomer may comprise: methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, cyclohexyl (meth)acrylate, allyl (meth)acrylate, dimethylamino ethyl methacrylate and/or butylamino ethyl (meth)acrylate.
  • the ethylenically unsaturated material such as of the copolymer additive when present with a polyvinyl butyral material, may comprise a vinyl material.
  • the vinyl material may comprise an aromatic group.
  • the vinyl material may comprise a styrene.
  • the ethylenically unsaturated material such as of the copolymer additive when present with a polyvinyl butyral material, may comprise an acrylamide material, such as an ether functional acrylamide material.
  • the acrylamide material may comprise an aliphatic group, such as an aliphatic group having at least three carbon atoms, or at least four carbon atoms.
  • the acrylamide material may comprise n-butoxymethyl acrylamide.
  • the ethylenically unsaturated material such as of the copolymer additive when present with a polyvinyl butyral material, may comprise acid functionality, such as by comprising methacrylic acid or acrylic acid.
  • the acid functionality may be at least partially neutralised with a neutralisation agent.
  • Suitable neutralisation agents may include ammonia or amine functional moieties: methyl ethanolamine, dimethylethanolamine (DMEA), trimethylamine, diethylene triamine.
  • the acid functionality may be at least 5% neutralised with a neutralisation agent.
  • the acid functionality on the further (co)polymer may be at least 25% neutralised with a neutralisation agent.
  • the acid functionality on the further (co)polymer may be at least 50% neutralised with a neutralisation agent.
  • the acid functionality on the further (co)polymer may be at least 75% neutralised with a neutralisation agent.
  • the ethylenically unsaturated material/copolymer additive may comprise hydroxyl functionality, such as by using a hydroxyl functional monomer.
  • the copolymer additive may be formed from >0.1 % of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive is formed, such as >0.3 wt% or S0.5 wt%.
  • the copolymer additive may be formed from ⁇ 90% of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive is formed, such as ⁇ 60 wt% or ⁇ 40 wt%.
  • the copolymer additive may be formed from 0.1 to 90 % of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive is formed, such as from 0.3 to 60 wt% or from 0.5 to 40 wt%.
  • the copolymer additive may be formed from 220% of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive is formed, such as 215 wt% or ⁇ 10 wt% or ⁇ 9 wt%.
  • the copolymer additive may be formed from 0.1 to 20 % of a monomer comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive is formed, such as from 0.3 to 15 wt% or from 0.5 to 10 wt% or from 0.5 to 9 wt%.
  • the copolymer additive may be formed from >50 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which the copolymer additive is formed, such as >60 wt% or >70 wt% or >75 wt%.
  • the copolymer additive may be formed from ⁇ 99.9 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which the copolymer additive is formed, such as ⁇ 99.7 wt% or ⁇ 99.5 wt%.
  • the copolymer additive may be formed from 50 to 99.9 % of ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group by total weight of the monomers from which the copolymer additive is formed, such as from 60 to 99.7. wt% or from 70 to 99.5 wt% or from 75 to 99.5 wt%.
  • the copolymer additive may be formed from ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group and a material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof in a weight ratio of from 99.9 wt% to 50 wt% ethylenically unsaturated material that does not comprise a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group to from 50 wt% to 0.1 wt% material comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group or precursor thereof by total weight of the monomers from which the copolymer additive
  • the copolymer additive may be formed from >5 % of a hydroxyl functional monomer by total weight of the monomers from which the copolymer additive is formed, such as 28 wt% or 210 wt%.
  • the copolymer additive may be formed from 240 % of a hydroxyl functional monomer by total weight of the monomers from which the copolymer additive is formed, such as 230 wt% or 220 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from >5 % of an acid functional monomer by total weight of the monomers from which the copolymer additive is formed, such as 210 wt% or >15 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 260% of an acid functional monomer by total weight of the monomers from which the copolymer additive is formed, such as ⁇ 40 wt% or ⁇ 30 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 5 to 60 % of an acid functional monomer by total weight of the monomers from which the copolymer additive is formed, such as from 10 to 40 wt% or from 15 to 30 wt%.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may be formed from ⁇ 9 % of an acid functional monomer by total weight of the monomers from which the copolymer additive is formed, such as 25 wt% or 21 wt% or 20.5wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from >1 % of an acrylamide monomer by total weight of the monomers from which the copolymer additive is formed, such as 23 wt% or 25 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from ⁇ 30% of an acrylamide monomer by total weight of the monomers from which the copolymer additive is formed, such as 20 wt% or ⁇ 15 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 1 to 30 % of an acrylamide monomer by total weight of the monomers from which the copolymer additive is formed, such as from 3 to 20 wt% or from 5 to 15 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 220 % of an aromatic group-containing monomer by total weight of the monomers from which the copolymer additive is formed, such as 30 wt% or 235 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 280% of an aromatic group-containing monomer by total weight of the monomers from which the copolymer additive is formed, such as 260 wt% or 250 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 20 to 80 % of an aromatic group-containing monomer by total weight of the monomers from which the copolymer additive is formed, such as from 30 to 60 wt% or from 35 to 50 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 220 % of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as 230 wt% or 235 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from ⁇ 80% of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as ⁇ 60 wt% or ⁇ 50 wt%.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be formed from 20 to 80 % of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as from 30 to 60 wt% or from 35 to 50 wt%.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may be formed from >50 % of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as >70 wt% or >75 wt% or >80 wt% or >90 wt%.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may be formed from ⁇ 99% of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as ⁇ 98 wt% or ⁇ 95 wt%.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may be formed from 50 to 99 % of an acrylic monomer by total weight of the monomers from which the copolymer additive is formed, such as from 70 to 98 wt% or from 80 to 95 wt% or from 90 to 95 wt%.
  • the ethylenically unsaturated material of the copolymer additive may comprise 220% of a cyclic vinyl material, such as an aromatic cyclic material, for example styrene, by total weight of the monomers from which the copolymer additive is formed, such as 210 wt% or 25 wt% or 21%.
  • the ethylenically unsaturated material may be substantially free of cyclic vinyl material, such as an aromatic cyclic material, for example styrene.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may have a number average molecular weight (Mn) of 2 , 000 Da, such as 2:2,000 Da or >3,000 Da or >3,100 Da.
  • Mn number average molecular weight
  • the copolymer additive may have a number average molecular weight of 210,000 Da, such as ⁇ 5,000 Da or ⁇ 4,900 Da, or ⁇ 4,500 Da.
  • the copolymer additive such as when present with a polyvinyl butyral material, may have a number average molecular weight (Mn) of 2:4,000 Da, such as 2:5,000 Da or >6,000 Da.
  • the copolymer additive may have a number average molecular weight of 215,000 Da, such as ⁇ 12,000 Da or ⁇ 10,000 Da.
  • the copolymer additive such as when present with a polyvinyl butyral material, may be a film former material.
  • the coating composition may comprise at least two different film former materials.
  • the coating composition may comprise a polyvinyl butyral film former material and a copolymer additive film former material.
  • the coating composition may comprise film former copolymer additive in an amount of 220% by total solid weight of film former material, such as >30wt% or >40wt%.
  • the coating composition may comprise film former copolymer additive in an amount of ⁇ 80% by total solid weight of film former material, such as ⁇ 70wt% or ⁇ 60wt%.
  • the coating composition may comprise film former copolymer additive in an amount of from 20 to 80% by total solid weight of film former material, such as from 30 to 70wt% or from 40 to 60wt%.
  • the copolymer additive may have any suitable glass transition temperature (Tg).
  • Tg glass transition temperature
  • the copolymer additive may have a Tg of >-50°C and/or ⁇ 200°C.
  • the copolymer additive may have any suitable gross hydroxyl value (OHV).
  • the copolymer additive such as when present with a polyvinyl butyral material, may have a gross OHV >0 and/or up to 50 mg KOH/g.
  • the copolymer additive such as when present with a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer, may have a gross OHV of >0 mg KOH/g, such as 210 mg KOH/g.
  • the copolymer additive may have a gross OHV of 2410 mg KOH/g, such as of 2200 mg KOH/g.
  • the copolymer additive may have a gross OHV of from >0 to 410 mg KOH/g, such as from 10 to 200 mg KOH/g.
  • the copolymer additive such as when present with a polyvinyl butyral material, may have any suitable acid value (AV).
  • the copolymer additive may have an AV of 25 KOH/g and/or ⁇ 200 KOH/g.
  • the copolymer additive may be prepared in the presence of a polymerisation initiator.
  • the polymerisation initiator may comprise an organic peroxide, such as a dialkyl peroxide and/or a peroxy ester, for example di-(tert-amyl) peroxide and/or tert-butyl peroctoate.
  • the polymerisation initiator may comprise a dialkyl peroxide.
  • the composition may comprise 21% of the copolymer additive by total solid weight of the composition, such as 2l .4wt%, or >1.5wt%.
  • the composition may comprise 240% of the copolymer additive by total solid weight of the composition, such as 230wt%, or 20wt%, or ⁇ 10wt%.
  • the composition may comprise from 1 to 40% of the copolymer additive by total solid weight of the composition, such as from 1 .4 to 30wt%, or from 1 .5 to 20wt%, or from 1 .5 to 10wt%.
  • the composition may comprise 210% of the copolymer additive by total solid weight of the composition, such as 220wt%, or >30wt%.
  • the composition such as when comprising a polyvinyl butyral material, may comprise ⁇ 80% of the copolymer additive by total solid weight of the composition, such as ⁇ 70wt%, or ⁇ 60wt%, or ⁇ 50wt%.
  • the composition may comprise from 10 to 80% of the copolymer additive by total solid weight of the composition, such as from 20 to 70wt%, or from 30 to 60wt %, or from 30 to 50wt%.
  • the composition may comprise >10% of film former material by total solid weight of the composition, such as >20wt%, or >30wt%, or >40wt%.
  • the composition may comprise 299.9% of film former material, by total solid weight of the composition, such as 299.5wt%, or 99wt%, or ⁇ 98wt%, or ⁇ 97wt%, or ⁇ 96wt%.
  • the composition may comprise from 10 to 99.9% of film former material, by total solid weight of the composition, such as from 20 to 99.9% or from 30 to 98wt%.
  • the composition may comprise >50% of film former material, by total solid weight of the composition, such as >60wt%, or >65wt%, or >70wt%.
  • the composition may comprise from 50 to 99.9% of the film former material, by total solid weight of the composition, such as from 60 to 98wt%, or from 65 to 98wt%.
  • the composition may comprise >50% of polyester (co)polymer and/or a (co)polymer(A)- (co)polymer(B) block and/or graft copolymer film former material, by total solid weight of the composition, such as >60wt%, or >65wt%, or >70wt%.
  • the coating composition may comprise >50% of polyester-(co)polymer(B) block and/or graft copolymer, by solid weight of the coating composition, such as >60wt%, or >65wt%, or >70wt%.
  • the composition may comprise from 50 to 99.9% of polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer film former material, by total solid weight of the composition, such as from 60 to 98wt%, or from 65 to 98wt%.
  • the composition may comprise from 50 to 99.9% of polyester-(co)polymer(B) block and/or graft copolymer film former material, by total solid weight of the composition, such as from 60 to 98wt%, or from 65 to 98wt%.
  • the coating composition may comprise >10% of a film former polyvinyl butyral material by solid weight of the coating composition, such as >20wt%, or >30wt%.
  • the coating composition may comprise ⁇ 80% of a film former polyvinyl butyral material by solid weight of the coating composition, such as ⁇ 70wt%, or ⁇ 60wt%.
  • the coating composition may comprise from 10 to 80% of a film former polyvinyl butyral material by solid weight of the coating composition, such as from 20 to 70wt%, or from 30 to 60wt%.
  • a polyester (co)polymer and/or a (co)polymer(A)-(co)polymer(B) block and/or graft copolymer film former material may comprise >70% of the total amount of film former material in the coating composition by total solid weight of film former material, such as >80wt% or >90wt%.
  • a polyvinyl butyral film former material may comprise S2O% of the total amount of film former material in the coating composition by total solid weight of film former material, such as >30wt% or >40wt%.
  • a polyvinyl butyral film former material may comprise ⁇ 80% of the total amount of film former material in the coating composition by total solid weight of film former material, such as ⁇ 70wt% or ⁇ 60wt%.
  • a polyvinyl butyral film former material may comprise from 20 to 80% of the total amount of film former material in the coating composition by total solid weight of film former material, such as from 30 to 70wt% or from 40 to 60wt%.
  • the coating composition may further comprise a liquid carrier, such as water and/or an organic solvent.
  • the coating composition may comprise water and/or a single solvent or a mixture of solvents.
  • the coating composition may comprise water, an organic solvent, a mixture of water and an organic solvent or a mixture of organic solvents.
  • the coating composition may comprise water and an organic solvent or water and a mixture of organic solvents.
  • the coating composition may be an aqueous coating composition.
  • An aqueous coating composition may represent a coating composition obtainable by dissolving and/or dispersing the film former copolymer in an aqueous medium.
  • An aqueous coating composition may be a coating composition comprising at least 10% water by total liquid carrier weight, such as at least 30 wt% or at least 50 wt%.
  • the film former copolymer may be substantially water dispersible.
  • the coating composition may comprise at least 40% water by total weight of the coating composition, such as at least 50 wt% or at least 55 wt%.
  • the coating composition may comprise up to 25% organic solvent, by total weight of the coating composition, such as up to 20 wt% or up to 15wt%.
  • the organic solvent may have sufficient volatility to essentially entirely evaporate from the coating composition during the curing process.
  • the curing process may be by heating at 130-230 °C for 1-15 minutes.
  • the coating composition may be an organic solventborne coating composition.
  • An organic solventborne coating composition may be a coating composition comprising more than 90% organic solvent by total liquid carrier weight, such as at least 95 wt%.
  • the organic solvent may have a sufficient volatility to essentially entirely evaporate from the coating composition during the curing process.
  • Suitable organic solvents include, but are not limited to the following: aliphatic hydrocarbons such as mineral spirits 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 SOLVESSO (RTM) trade name; alcohols such as ethanol; n- propanol; isopropanol; n-butanol; pentanol; amyl alcohol; 1-methoxy-2-propanol; and butoxy ethanol; ketones such as acetone; cyclohexanone; methylisobutyl ketone; methyl ethyl ketone; esters such as ethyl acetate; butyl acetate; n-hexyl acetate; RHODIASOLV (RTM) RPDE (a blend of succinic and adipic esters commercially available from Rh
  • the copolymer additive and/or film former material may be dissolved or dispersed in the said solvent during and/or after its formation.
  • the coating composition may comprise other optional materials well known in the art of formulating coatings, such as colorants, plasticizers, abrasion-resistant particles, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic co-solvents, reactive diluents, catalysts, grind vehicles, lubricants, waxes and other customary auxiliaries.
  • colorants such as colorants, plasticizers, abrasion-resistant particles, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic co-solvents, reactive diluents, catalysts, grind vehicles, lubricants, waxes and other customary auxiliaries.
  • colorant means any substance that imparts color and/or other opacity and/or other visual effect to the composition.
  • the colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes.
  • a single colorant or a mixture of two or more colorants can be used in the coatings of the present disclosure. Suitable colorants are listed in U.S. Patent No. 8,614,286, column 7, line 2 through column 8, line 65, which is incorporated by reference herein.
  • Colorant suitable for packaging coatings are those approved for food contact, such as titanium dioxide; iron oxides, such as black iron oxide; aluminium paste; aluminium powder such as aluminium flake; carbon black; ultramarine blue; phthalocyanines, such as phthalocyanine blue and phthalocyanine green; chromium oxides, such as chromium green oxide; graphite fibrils; ferried yellow; quindo red; and combinations thereof, and those listed in Article 178.3297 of the Code of Federal Regulations, which is incorporated by reference herein.
  • the colorant when present, may be used in the coating composition in any suitable amount.
  • the coating composition may comprise up to 90 wt%, such as up to 50 wt%, or even up to 10 wt% colorant, when present, based on the total solid weight of the coating composition.
  • Suitable lubricants will be well known to the person skilled in the art. Suitable examples of lubricants include, but are not limited to the following: carnauba wax and polyethylene type lubricants.
  • the coating composition may comprise at least 0.01 wt% lubricant, when present, based on the total solid weight of the coating composition.
  • Surfactants may optionally be added to the coating composition in order to aid in flow and wetting of the substrate. Suitable surfactants will be well known to the person skilled in the art.
  • the surfactant when present, may be chosen to be compatible with food and/or beverage container applications. Suitable surfactants include, but are not limited to the following: alkyl sulphates (e.g., sodium lauryl sulphate); ether sulphates; phosphate esters; sulphonates; and their various alkali, ammonium, amine salts; aliphatic alcohol ethoxylates; alkyl phenol ethoxylates (e.g. nonyl phenol polyether); salts and/or combinations thereof.
  • the coating composition may comprise from 0.01 wt% to 10 wt%, such as from 0.01 to 5 wt%, or even from 0.01 to 2 wt% surfactant, when present, based on the total solid weight of the coating composition.
  • the coating composition may comprise a crosslinking material.
  • the coating composition may comprise any suitable crosslinking material. Suitable crosslinking materials will be well known to the person skilled in the art.
  • the crosslinking material may be operable to crosslink the film former material.
  • the crosslinking material may be a single molecule, a dimer, an oligomer, a (co)polymer or a mixture thereof.
  • the crosslinking material may be a dimer or trimer.
  • Suitable crosslinking materials include, but are not limited to: phenolic resins (or phenolformaldehyde resins); aminoplast resins (or triazine-formaldehyde resins); amino resins; epoxy resins; isocyanate resins; beta-hydroxy (alkyl) amide resins; alkylated carbamate resins; polyacids; anhydrides; organometallic acid-functional materials; polyamines; and/or polyamides and combinations thereof.
  • Suitable examples of phenolic resins are those formed from the reaction of a phenol with an aldehyde or a ketone, such as from the reaction of a phenol with an aldehyde, such as from the reaction of a phenol with formaldehyde or acetaldehyde, or even from the reaction of a phenol with formaldehyde.
  • Non-limiting examples of phenols which may be used to form phenolic resins are phenol, butyl phenol, xylenol and cresol.
  • phenolic resins may be of the resol type.
  • resol type we mean resins formed in the presence of a basic (alkaline) catalyst and optionally an excess of formaldehyde.
  • Suitable examples of commercially available phenolic resins include, but are not limited to those sold under the trade name PHENODUR (RTM) commercially available from Allnex, such as PHENODUR EK-827, PHENODUR VPR1785, PHENODUR PR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODUR PR612 or PHENODUR PH2024; resins sold under the trade name BAKELITE (RTM) commercially available from Sumitomo Bakelite co., ltd., such as BAKELITE 6582 LB, BAKELITE 6535, BAKELITE PF9989 or BAKELITE PF6581 ; SFC 112 commercially available from SI Group; DUREZ (RTM) 33356 commercially available from SHHPP; ARALINK (RTM) 40- 852 commercially available from Bitrez; or combinations thereof.
  • PHENODUR RTM
  • RTM trade name commercially available from Allnex, such
  • Suitable examples of isocyanate resins include, but are not limited to the following: isophorone diisocyanate (IPDI), such as those sold under the trade name DESMODUR (RTM) commercially available from Cevstro, for example DESMODUR VP-LS 2078/2 or DESMODUR PL 340 or those sold under the trade name VESTANAT (RTM) commercially available from Evonik, for example VESTANANT B 1370, VESTANAT B 118 6A or VESTANAT B 1358 A; blocked aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), such as those sold under the trade name DESMODUR (RTM) commercially available from Covestro, for example DESMODUR BL3370 or DESMODUR BL 3175 SN, those sold under the trade name DURANATE (RTM) commercially available from Asahi KASEI, for example DURANATE MF-K60X, those sold under the trade name TO
  • the crosslinking material may contain nitrogen.
  • the crosslinking material may be in the form of an amine or amide material.
  • the crosslinking material may comprise a hydroxyl substituted amine or amide material.
  • the crosslinking material may comprise a hydroxyalkylamide material, such as a p- hydroxyalkylamide material.
  • the crosslinking material may comprise a commercially available p-hydroxyalkylamide crosslinking, such as, for example, PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N’,N’-tetrakis(2-hydroxypropyl)adipamide.
  • PRIMID XL-552 available from EMS
  • PRIMID QM-1260 available from EMS Chemie
  • N,N,N’,N’-tetrakis(2-hydroxypropyl)adipamide such as, for example, PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N’,N’-tetrakis(2-hydroxypropyl)adipamide.
  • the crosslinking material may be in the form of a urea material.
  • the crosslinking material may comprise a hydroxyl substituted urea material.
  • the crosslinking material may comprise a hydroxy functional alkyl polyurea material.
  • the hydroxy functional alkyl polyurea material may comprise a material according to formula (I): wherein R comprises an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, polyetheramine moiety, and/or polymeric moiety different from a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently a hydrogen, alkyl having a carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.
  • R comprises an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, polyetheramine moiety, and/or polymeric moiety different from a polyetheramine and having an Mn of 500 or greater
  • each R1 is independently a hydrogen, alkyl having a carbon, or a hydroxy functional alky
  • the hydroxy functional alkyl polyurea material may comprise a material according to formula (II): wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, polyetheramine moiety, and/or polymeric moiety different from a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently a hydrogen, an alkyl having a carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxyl functional alkyl having 2 or more carbons; and n is 2-6.
  • R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, poly
  • Suitable examples of aminoplast resins include those which are a reaction product of a reaction mixture comprising a triazine such as melamine or benzoguanamine and formaldehyde. These condensates may be etherified, such as with methanol, ethanol, butanol or mixtures thereof.
  • a triazine such as melamine or benzoguanamine and formaldehyde.
  • These condensates may be etherified, such as with methanol, ethanol, butanol or mixtures thereof.
  • aminoplast resins see “The Chemistry and Applications of Amino Crosslinking agents or Aminoplast”, Vol. V, Part 11 , page 21 ff., edited by Dr. Oldring; John Wiley & Sons/Cita Technology Limited, London, 1998.
  • Suitable examples of commercially available aminoplast resins include, but are not limited to, those sold under the trade name MAPRENAL (registered trade mark), such as MAPRENAL MF980 (commercially available from Ineos); those sold under the trade name CYMEL (registered trade mark), such as CYMEL 303 and CYMEL 1128 (available from Allnex Industries); and combinations thereof.
  • MAPRENAL registered trade mark
  • CYMEL registered trade mark
  • CYMEL 1128 available from Allnex Industries
  • the crosslinking material may comprise material according to formula (III) wherein Ri represents hydrogen, alkyl (such as Ci to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl), or — NReR?;
  • R2 to R? each independently represent hydrogen, alkyl (such as Ci to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl) or — CHRsORg; wherein Rs and Rg each independently represent hydrogen, alkyl (such as Ci to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl), alkoxyalkyl (such as C2 to C40 alkoxyalkyl) or an alkaryl (such as C5 to C25 alkaryl); wherein at least one of R2 to Rs, or R2 to Ry when present, is — CHRsORg, for example all of R2 to Rs, or R2 to R7 when present, may be — CHRsORg.
  • R1 may be Ci to C20 alkyl, C4 to C24 aryl, Cs to C25 aralkyl, or — NRsR?; such as C4 to C24 aryl or Cs to C25 aralkyl, or C4 to C24 aryl, such as C4 to C12 aryl, such as Cs aryl.
  • R1 may be — NReRy.
  • R2 to Ry when present as applicable, may each be independently hydrogen, Ci to C20 alkyl, C4 to C24 aryl or — CHRsORg; such as hydrogen, Ci to C20 alkyl or — CHRsORg, such as hydrogen, Ci to C10 alkyl or — CHRsORg; such as Ci to C5 alkyl or — CHRsORg, such as — CHRsORg.
  • R2 to Ry when present as applicable, may each be independently hydrogen, Ci to C20 alkyl, C4 to C24 aryl or — CHRsORg; such as hydrogen, Ci to C20 alkyl or — CHRsORg, such as hydrogen, Ci to C10 alkyl or — CHRsORg; such as Ci to C5 alkyl or — CHRsORg, such as — CHRsORg, and Rs may be independently be hydrogen, Ci to C20 alkyl, C4 to C24 aryl, Cs to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or Cs to C25 alkaryl, such as hydrogen, Ci to C20 alkyl, such as hydrogen; and Rg may be hydrogen, Ci to C20 alkyl, C4 to C24 aryl, Cs to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or Cs to C25 alkaryl, such as hydrogen, Ci
  • the crosslinking material according to formula (III) may be a reaction product of a reaction mixture comprising a triazine such as melamine or benzoguanamine and formaldehyde. These condensates may be etherified, such as with methanol, ethanol, butanol or mixtures thereof.
  • a triazine such as melamine or benzoguanamine and formaldehyde.
  • These condensates may be etherified, such as with methanol, ethanol, butanol or mixtures thereof.
  • aminoplast resins see “The Chemistry and Applications of Amino Crosslinking agents or Aminoplast”, Vol. V, Part 11 , page 21 ff . , edited by Dr. Oldring; John Wiley & Sons/Cita Technology Limited, London, 1998.
  • the crosslinking material according to formula (III) may comprise melamine or derivatives thereof, such as butylated and/or methylated melamine; and/or benzoguanamine or derivatives thereof, such as butylated and/or methylated benzoguanamine.
  • the crosslinking material according to formula (III) may comprise benzoguanamine or derivatives thereof, such as butylated and/or methylated benzoguanamine.
  • the crosslinking material according to formula (III) may comprise at least partially butylated benzoguanamine.
  • the crosslinking material, such as according to formula (III), may be self-curing.
  • the crosslinking material according to formula (III) may comprise a self-curing melamine, benzoguanamine or derivative thereof, such as a self-curing at least partially butylated benzoguanamine.
  • self-curing with respect to the crosslinking material may mean a crosslinking material that is operable to cure in the coating composition in the absence of a curing catalyst additive that is suitable to catalyse crosslinking reactions between the film former and the crosslinking material.
  • a coating composition comprising a self-curing crosslinking material may provide good or improved adhesion.
  • Such a coating composition may provide good or improved adhesion in combination with maintained and/or improved properties such as enamel rating, solvent fraction, blush and/or feathering.
  • the crosslinking material may comprise those which are the reaction product of a reaction mixture comprising a triazine, such as melamine or benzoguanamine, and formaldehyde.
  • the crosslinking material may comprise benzoguanamine or a derivative thereof.
  • the benzoguanamine or derivative thereof may comprise commercially available benzoguanamine or derivative thereof.
  • suitable examples of commercially available benzoguanamine and its derivatives include, but are not limited to benzoguanamine- formaldehyde based materials such as those sold under the trade name CYMEL (registered trade mark), for example CYMEL 1123 (commercially available from Allnex Industries), those sold under the trade name ITAMIN (registered trade mark), for example ITAMIN BG143 (commercially available from Galstaff Multiresine) or those sold under the trade name MAPRENAL (registered trade mark), for example, MAPRENAL BF892 and MAPRENAL BF 892/68B (commercially available from Ineos); glycoluril based materials, such as those sold under the trade name CYMEL (registered trade mark), for example, CYMEL 1170 and CYMEL 1172 (commercially available from Allnex); and combinations thereof.
  • CYMEL registered trade mark
  • the benzoguanamine or derivative thereof may comprise benzoguanamine-formaldehyde based materials sold under the trade name MAPRENAL (registered trade mark).
  • the benzoguanamine or derivative thereof may comprise MAPRENAL BF892, MAPRENAL BF 892/68B and/or MAPRENAL MF-984 (commercially available from Ineos).
  • the coating composition may comprise an aminoplast crosslinker, such as a benzoguanamine or a derivative thereof, and a further crosslinker, such as a phenolic resin.
  • an aminoplast crosslinker such as a benzoguanamine or a derivative thereof
  • a further crosslinker such as a phenolic resin.
  • the crosslinking material may be present in the coating composition in any suitable amount.
  • the coating composition may comprise at least 0.5 wt% crosslinking material based on the total solid weight of the coating composition. Such as at least 1 wt%, at least 5 wt%, at least 10 wt% crosslinking material based on the total solid weight of the coating composition.
  • the coating composition may comprise up to 70wt% crosslinking material based on the total solid weight of the coating composition. Such as up to 60wt%, up to 50wt%, up to 40wt%, up to 30wt%, up to 25wt%, or up to 20wt% crosslinking material based on the total solid weight of the coating composition.
  • the coating composition may comprise from 0.5 to 90wt%, or 1 to 90wt%, such as from 1 to 80wt%, such as from 1 to 70wt%, such as from 1 to 60wt%, such as from 1 to 50wt%, such as from 1 to 40wt%, such as from 1 to 30wt%, or even from 1 to 25wt% crosslinking material based on the total solid weight of the coating composition.
  • the coating composition may comprise from 5 to 90wt%, such as from 5 to 80wt%, such as from 5 to 70wt%, such as from 5 to 60wt%, such as from 5 to 50wt%, such as from 5 to 40wt%, such as from 5 to 30wt%, or even from 5 to 25wt% crosslinking material based on the total solid weight of the coating composition.
  • the coating composition may comprise from 10 to 90wt%, such as from 10 to 80wt%, such as from 10 to 70wt%, such as from 10 to 60wt%, such as from 10 to 50wt%, such as from 10 to 40wt%, such as from 10 to 30wt%, or even from 10 to 25wt%, or 10 to 20wt%, crosslinking material based on the total solid weight of the coating composition.
  • the coating compositions may further comprise a catalyst.
  • a catalyst Any catalyst suitable to catalyse crosslinking reactions between the film former and/or any crosslinking material may be used. Suitable catalysts will be well known to the person skilled in the art.
  • the catalyst may be a non- metal or a metal catalyst or a combination thereof.
  • Suitable non-metal 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 catalyst such as NACURE XC 235 (commercially available from King Industries); and combinations thereof.
  • Suitable metal catalysts will be well known to the person skilled in the art.
  • Suitable metal catalysts include, but are not limited to the following: tin containing catalysts, such as monobutyl tin tris (2-ethylhexanoate); zirconium containing catalysts, such as KKAT (RTM) 4205 (commercially available from King Industries); titanate based catalysts, such as tetrabutyl titanate TnBT (commercially available from Sigma Aldrich); and combinations thereof.
  • tin containing catalysts such as monobutyl tin tris (2-ethylhexanoate
  • zirconium containing catalysts such as KKAT (RTM) 4205 (commercially available from King Industries)
  • titanate based catalysts such as tetrabutyl titanate TnBT (commercially available from Sigma Aldrich); and combinations thereof.
  • Suitable examples of catalysts may include, but are not limited to the following: metal compounds such as stannous octoate; stannous chloride; butyl stannoic acid (hydroxy butyl tin oxide); monobutyl tin tris (2-ethylhexanoate); chloro butyl tin dihydroxide; tetra-n-propyl titanate; tetra-n-butyl titanate; zinc acetate; acid compounds such as phosphoric acid; para-toluene sulphonic acid; dodecyl benzene sulphonic acid (DDBSA) such as blocked DDBSA, tetra alkyl zirconium materials, antimony trioxide, germanium dioxide and combinations thereof.
  • the catalyst may comprise dodecyl benzene sulphonic acid (DDBSA), such as blocked DDBSA.
  • the catalyst when present, may be used in the coating composition in any suitable amount.
  • the catalyst may be present in the coating composition in an amounts of so.001% by solid weight of the coating composition coating composition, such as ⁇ 0.01%, such as so.025% by solid weight of the coating composition.
  • the catalyst may be present in the coating composition in an amount of 21% by solid weight of the coating composition coating composition, such as 20.7%, such as 20.5% by solid weight of the coating composition.
  • the catalyst may be present in the coating composition in amounts from 0.001 to 1 % by solid weight of the coating composition coating composition, such as from 0.01 to 0.7%, such as from 0.025 to 0.5% by solid weight of the coating composition.
  • the coating composition may comprise 21 % by solid weight of the coating composition of a curing catalyst additive, such as 20.7 wt%, 20.5 wt%, 20.25 wt%, 20.1 wt%, 20.05 wt%, 20.025 wt%, 20.01 wt% or 20.001 wt%.
  • curing catalyst additive means a component added to the composition, in addition where applicable to the copolymer additive of the disclosure comprising a sulfonic acid-, a sulfate-, a phosphonic acid- and/or a phosphate- functional group, that is operable to catalyse crosslinking reactions between the film former and/or any crosslinking agent.
  • the curing catalyst additive may be a metal compound such as stannous octoate; stannous chloride; butyl stannoic acid (hydroxy butyl tin oxide); monobutyl tin tris (2- ethylhexanoate); chloro butyl tin dihydroxide; tetra-n-propyl titanate; tetra-n-butyl titanate; zinc acetate; an acid compound such as phosphoric acid; para-toluene sulphonic acid; dodecyl benzene sulphonic acid (DDBSA) such as blocked DDBSA, tetra alkyl zirconium materials, antimony trioxide, germanium dioxide and combinations thereof.
  • DBSA dodecyl benzene sulphonic acid
  • the curing catalyst additive may be dodecyl benzene sulphonic acid and/or para-toluene sulphonic acid.
  • the curing catalyst additive may be a small molecule curing catalyst additive.
  • a small molecule curing catalyst additive may be a non-polymeric curing catalyst additive and/or a curing catalyst additive having a molecular weight of ⁇ 1 ,000 Da, such as 2800 Da or 2500 Da.
  • the coating compositions may be substantially free, may be essentially free or may be completely free of a curing catalyst additive. “Substantially free” refers to coating compositions, or components thereof, containing less than 1000 parts per million (ppm) of a curing catalyst additive.
  • Essentially free refers to coating compositions, or components thereof, containing less than 100 ppm of any of a curing catalyst additive. “Completely free” refers to coating compositions, or components thereof, containing less than 20 parts per billion (ppb) of a curing catalyst additive.
  • the coating composition may have any suitable solids content.
  • the coating composition may have a solids content of 2 0 by weight of the coating composition, such as ⁇ 20 or >30%.
  • the coating composition may have a solids content of 280% by weight of the coating composition, such as 270 wt% or 265 wt%.
  • the coating composition may have a solids content of from 10 to 80% by weight of the coating composition, such as from 20 to 70wt% or from 30 to 65 wt%.
  • the coating composition may have a Brookfield viscosity of at least 30 centipoise, such as at least 35 centipoise or at least 40 centipoise.
  • the coating composition may have a Brookfield viscosity of up to 35,000 centipoise, such as up to 30,000 centipoise, or up to 27,000 centipoise.
  • the coating composition such as a coating composition comprising a film former polyvinyl butyral material, may have a Brookfield viscosity of up to 2,000 centipoise, such as up to 1 ,500 centipoise, or up to 1,200 centipoise.
  • the coating composition such as a coating composition comprising a film former polyvinyl butyral material, may have a Brookfield viscosity of from 30 to 2,000 centipoise, such as from 35 to 1 ,500 centipoise or from 40 to 1 ,200 centipoise. As used herein, the viscosity was measured using an RV Brookfield viscometer with spindle 6 at 30 rpm.
  • a cured film formed from the coating composition of the present disclosure having a film weight of 7 mg/in 2 may have an enamel rating after pack of 216 mA, such as 215 mA or 214 mA.
  • the enamel rating after pack was measured as follows: 47 grams of the stock solution of L-85 was added to the can followed by the addition of 308 grams of carbonated water. A 202 type seamer was then used to seam an end onto the can. The can was then placed upside down (inverted) into a 100° F. (38° C.) incubator for 6 days). The can was then removed from the incubator, opened, and then measured using the Waco Enamel Rater test in which electrolyte was added to the plastic cup of Waco Enamel Rater, the can end was fitted onto the beveled end of the cup, and a vacuum applied to hold the end securely on the cup. When the cup was inverted, the electrode and can end were immersed in the electrolyte and the reading was displayed on the Enamel Rater.
  • a cured film formed from the coating composition of the present disclosure may have a solvent fraction of 216%, such as 212% or 29%.
  • a cured film formed from the coating composition of the present disclosure may have a feathering of 22.5 mm, such as 20.6 mm or 20.5 mm.
  • the feathering property of the coatings was measured as follows: A chromium pretreated aluminium panels (Henkel 702N, AA5182 Alloy) having a thickness of 0.21 mm was coated with a coating composition to give a film weight 7.0 mg/in 2 . The panel was then baked in a three zone coil oven to a peak metal temperature of 240°C. The panel was then cut into a 50.8 mm by 88.9 mm piece, with the substrate grain running perpendicular to the long length of the cut panel. The test panel coated side up was then inserted between the score tool and the anvil in a Carver press. The long edge of the panel was abutted against the guide block on the inside of the press.
  • FIG. 1 Shown in Figure 1 is a schematic of the coated panel (100) comprising the score line of the simulated tab (102).
  • the simulated tab (102) extended perpendicularly to the long length (I) of the panel.
  • the terminal points (104, 106) of the score line (which collectively form the front of the simulated tab, i.e., the portion of the tab that was first opened) were both arranged at an edge of the long length (I) of the panel.
  • the dimensions of the simulated tab (102) were: A (48.0 mm); B (11.3 mm); C (24.0 mm); D (18.00 mm); E and F area (89.4 mm 2 ); and G (10.6 mm).
  • Lengths D extended from the upper terminal point of respective length C to the left and right vertex of circles E and F, respectively.
  • Length G extended between the upper vertex of circles E and F.
  • the panel was then removed from the press and two spaced parallel cuts were formed in the panel at the front end of the simulated tab along the score line. Each cut extended inward into the panel, perpendicularly to the long length, starting from the terminal points (104 and 106) of the score line.
  • the cuts extended 6.4 mm into the panel along the respective portion of the score line and were spaced 11 .3 mm apart.
  • the panel was then fully immersed in deionized water for 30 minutes at 250 °F (121 °C).
  • the panel was then removed and immediately submerged in 22°C DI water for 2 seconds.
  • the panel was then removed from the deionized water.
  • the cut portion of the simulated tab was bent 180° toward the coated face of the panel.
  • the panel was then inserted into a vice where the panel was held along the long length, with the edge from which the score line extended being held in the vice.
  • Pliers were then used to grip the cut portion of the simulated tab and then to pull the cut portion of the tab 180° across the coated face of the panel toward the opposite end of the tab at a rate of 1 second/cm. Feathering was then measured using a digital Microscope. The length of the coating that extended furthest into the tab opening was measured in mm and recorded.
  • a “cured film” as used to measure properties of the film described herein means a film formed as follows.
  • the coating composition was drawn down with a wire wound bar over a chromium pretreated aluminium panel (Henkel 702N, AA5182 Alloy) to give a dry film weight of 6.5-7.5 milligrams/square inch (msi), unless indicated otherwise.
  • the panels were then baked in a three zone coil oven (249/326/293°C) to a peak metal temperature of 240°C.
  • the cured film used to measure properties described herein may be a dry film or a wet film.
  • dry film refers to a film that was formed by curing the coating composition to form a cured film
  • wet film refers to a film that was formed by curing the coating composition to form a cured film, which was then soaked in commercially available Coca Cola Classic at 38°C (100°F) for 24 hours before testing.
  • the coating compositions of the present disclosure may be substantially free, may be essentially free or may be completely free of bisphenol A (BPA) and derivatives thereof.
  • Derivatives of bisphenol A include, for example, bisphenol A diglycidyl ether (BADGE).
  • the coating compositions of the present disclosure may also be substantially free, may be essentially free or may be completely free of bisphenol F (BPF) and derivatives thereof.
  • Derivatives of bisphenol F include, for example, bisphenol F diglycidyl ether (BPFG).
  • BPFG bisphenol F diglycidyl ether
  • the compounds or derivatives thereof mentioned above may not be added to the composition intentionally but may be present in trace amounts because of unavoidable contamination from the environment.
  • “Substantially free” refers to coating compositions, or components thereof, containing less than 1000 parts per million (ppm) of any of the compounds or derivatives thereof mentioned above. “Essentially free” refers to coating compositions, or components thereof, containing less than 100 ppm of any of the compounds or derivatives thereof mentioned above. By “Completely free” refers to coating compositions, or components thereof, containing less than 20 parts per billion (ppb) of any of the compounds or derivatives thereof mentioned above.
  • the coating compositions of the present disclosure may be substantially free, may be essentially free or may be completely free of dialkyltin compounds, including oxides or other derivatives thereof.
  • dialkyltin compounds include, but are not limited to the following: dibutyltindilaurate (DBTDL); dioctyltindilaurate; dimethyltin oxide; diethyltin oxide; dipropyltin oxide; dibutyltin oxide (DBTO); dioctyltinoxide (DOTO) or combinations thereof.
  • substantially free we mean to refer to coating compositions containing less than 1000 parts per million (ppm) of any of the compounds or derivatives thereof mentioned above.
  • essentially free we mean to refer to coating compositions containing less than 100 ppm of any of the compounds or derivatives thereof mentioned above.
  • completely free we mean to refer to coating compositions containing less than 20 parts per billion (ppb) of any of the compounds or derivatives thereof.
  • the coating compositions may be substantially free, may be essentially free or may be completely free of formaldehyde. “Substantially free” refers to coating compositions, or components thereof, containing less than 1000 parts per million (ppm) of formaldehyde. “Essentially free” refers to coating compositions, or components thereof, containing less than 100 ppm of any of formaldehyde. “Completely free” refers to coating compositions, or components thereof, containing less than 20 parts per billion (ppb) of formaldehyde.
  • the coating compositions and/or layers deposited from the same, as well as any pretreatment layer, primer layer or topcoat layer may be substantially free of chromium or chromium-containing compounds meaning that chromium or chromium-containing compounds are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition; this may further include that chromium or chromium-containing compounds are not present in an aqueous or powder composition and/or layers deposited from the same, as well as any pretreatment layer, primer layer or topcoat layer, in such a level that they cause a burden on the environment.
  • substantially free means that a coating composition and/or layers deposited from the same, as well as any pretreatment layer, primer layer or topcoat layer, contain less than 10 ppm of chromium, based on total solids weight of the composition, the layer, or the layers, respectively, if any at all.
  • essentially free means that a coating composition and/or layers deposited from the same, as well as any pretreatment layer, primer layer or topcoat layer, contain less than 1 ppm of chromium, based on total solids weight of the composition or the layer, or layers, respectively, if any at all.
  • the coating compositions may be applied to the substrate by any suitable method. Suitable methods of applying the coating compositions will be well known to a person skilled in the art. Suitable application methods for the coating compositions include, but are not limited to, the following: spraying; electrostatic spraying; dipping; rolling; brushing; and the like. The coating compositions may be applied to a substrate by electrocoating.
  • the coating compositions may be applied to the substrate, or a portion thereof, as a single layer or as part of a multi layer system.
  • the coating compositions may be applied as a single layer.
  • the coating compositions may be applied to an uncoated substrate.
  • an uncoated substrate extends to a surface that is cleaned prior to application.
  • the coating compositions may be applied on top of another paint layer as part of a multi layer system.
  • the coating compositions may be applied on top of a primer.
  • the coating compositions may form an intermediate layer or a top coat layer.
  • the coating compositions may be applied as the first coat of a multi coat system.
  • the coating compositions may be applied as an undercoat or a primer. The second, third, fourth etc.
  • coats may comprise any suitable paint such as those containing, for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins or combinations thereof.
  • the second, third, fourth etc. coats may comprise polyester resins.
  • the second, third, fourth etc. coats may be a liquid coating or a powder coating.
  • the coating compositions may be applied before or after forming the article, such as the packaging.
  • the coating compositions may be applied to metal substrate which is then shaped and formed into a metal article, or the coating composition may be applied to the preformed article.
  • the coating compositions may be applied to a substrate once or multiple times.
  • Powder coating compositions may be applied by any suitable method. Methods of applying said powder coating compositions will be well known to a person skilled in the art. Suitable application methods include, such as electrodeposition, or applied by ultra corona discharge for example. The powder coating compositions may be applied by ultra corona discharge.
  • the coating compositions may be applied to any suitable dry film thickness.
  • the coating compositions may be applied to a dry film thickness from 1 to 100 microns (pm), such as from 1 to 75 pm, such as from 1 to 50 pm, such as from 1 to 40 pm, such as from 1 to 20 pm, or even from 1 to 10 pm.
  • pm microns
  • the coating compositions may be cured by any suitable method.
  • the coating composition may be cured by heat curing, radiation curing or by chemical curing, such as by heat curing.
  • the coating composition when heat cured, may be cured at any suitable temperature.
  • the coating composition when heat cured, may be cured to a peak metal temperature (PMT) of 100 to 350°C, such as 150 to 350°C, such as from 175 to 320°C, such as from 190 to 300°C, or even from 200 to 280°C.
  • peak metal temperature and like terms as used herein, is meant unless specified otherwise the maximum temperature reached by the metal substrate during exposure to a heat during the heat curing process.
  • the peak metal temperature (PMT) is the maximum temperature reached by the metal substrate and not the temperature which is applied thereto.
  • the temperature reached by the metal substrate may be lower than the temperature which is applied thereto or may be substantially equal to the temperature which is applied thereto.
  • the temperature reached by the metal substrate may be lower that the temperature which is applied thereto.
  • Curing the coating compositions may form a cured film.
  • a liquid coating composition may be electrophoretically deposited upon any electrically conductive substrate.
  • Suitable substrates include metal substrates, metal alloy substrates, and/or substrates that have been metallized, such as nickel-plated plastic. Additionally, substrates may comprise non-metal conductive materials including composite materials such as, for example, materials comprising carbon fibers or conductive carbon.
  • the metal or metal alloy may comprise, for example, cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvanealed steel, nickel-plated steel, and steel plated with zinc alloy.
  • the substrate may comprise an aluminium alloy.
  • Non-limiting examples of aluminium alloys include the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminium alloys and cast aluminium alloys, such as, for example, the A356 series.
  • the substrate may comprise a magnesium alloy.
  • magnesium alloys of the AZ31 B, AZ91 C, AM60B, or EV31 A series also may be used as the substrate.
  • the substrate may also comprise other suitable non-ferrous metals such as titanium or copper, as well as alloys of these materials.
  • the part to be coated may be in the shape of a cylinder, such as a pipe, including, for example, a cast iron or steel pipe.
  • the metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part.
  • the substrate may also comprise conductive or non- conductive substrates at least partially coated with a conductive coating.
  • the conductive coating may comprise a conductive agent such as, for example, graphene, conductive carbon black, conductive polymers, or conductive additives. It will also be understood that the substrate may be pretreated with a pretreatment solution.
  • a pretreatment solution include a zinc phosphate pretreatment solution such as, for example, those described in U.S. Patent Nos.
  • a zirconium containing pretreatment solution such as, for example, those described in U.S. Patent Nos. 7,749,368 and 8,673,091.
  • a pretreatment solution include those comprising trivalent chromium, hexavalent chromium, lithium salts, permanganate, rare earth metals, such as yttrium, or lanthanides, such as cerium.
  • a suitable surface pretreatment solution is a sol-gel, such as those comprising alkoxy-silanes, alkoxy-zirconates, and/or alkoxy-titanates.
  • the substrate may be a non-pretreated substrate, such as a bare substrate, that is not pretreated by a pretreatment solution.
  • the substrate may optionally be subjected to other treatments prior to coating.
  • the substrate may be cleaned, cleaned and deoxidized, anodized, acid pickled, plasma treated, laser treated, or ion vapor deposition (IVD) treated.
  • ILD ion vapor deposition
  • a liquid composition of the disclosure may be utilized in a coating layer that is part of a multi-layer coating composite comprising a substrate with various coating layers.
  • the coating layers may optionally include a pretreatment layer, such as a phosphate layer (e.g., zinc phosphate layer) or metal oxide layer (e.g., zirconium oxide layer), a coating layer which results from an aqueous composition of the disclosure, optionally primer layer(s) and suitable topcoat layer(s) (e.g., base coat, clear coat layer, pigmented monocoat, and color-plus-clear composite compositions).
  • a pretreatment layer such as a phosphate layer (e.g., zinc phosphate layer) or metal oxide layer (e.g., zirconium oxide layer)
  • primer layer(s) and suitable topcoat layer(s) e.g., base coat, clear coat layer, pigmented monocoat, and color-plus-clear composite compositions.
  • suitable additional coating layers include any of those known in the art, and each independently may be waterborne, solventborne, in solid particulate form (i.e., a powder coating composition), or in the form of a powder slurry.
  • the additional coating compositions may comprise a film-former polymer, crosslinking material and, if a colored base coat or monocoat, pigment.
  • the primer layer(s) may optionally be disposed between the electrocoating layer and the topcoat layer(s). Alternatively, the topcoat layer(s) may be omitted such that the composite comprises the coating layer of the disclosure and primer layer(s).
  • the topcoat layer(s) may be applied directly onto the coating layer of the disclosure.
  • the substrate may lack a primer layer such that the composite comprises the coating layer of the disclosure and topcoat layer(s).
  • a basecoat layer may be applied directly onto at least a portion of the coating layer of the disclosure.
  • any of the topcoat layers may be applied onto an underlying layer despite the fact that the underlying layer has not been fully cured.
  • a clearcoat layer may be applied onto a basecoat layer even though the basecoat layer has not been subjected to a curing step (wet-on-wet). Both layers may then be cured during a subsequent curing step thereby eliminating the need to cure the basecoat layer and the clearcoat layer separately.
  • the coating composition may be a powder coating composition.
  • the powder coating composition may be electrostatically applied. Electrodeposition generally involves drawing the coating composition from a fluidized bed and propelling it through a corona field. The particles of the coating composition become charged as they pass through the corona field and are attracted to and deposited upon the electrically conductive substrate, which is grounded. As the charged particles begin to build up, the substrate becomes insulated, thus limiting further particle deposition.
  • the coating compositions may be applied to the substrate by spraying.
  • the coating compositions may be spray compositions.
  • spray composition and like terms as used herein is meant, unless specified otherwise, that the coating is suitable to be applied to a substrate by spraying, i.e., is sprayable.
  • the coating compositions may be applied to any suitable substrate.
  • the substrate may be formed of metal, plastic, composite and/or wood.
  • the substrate may be a metal substrate.
  • Suitable metals include, but are not limited to, the following: steel; tinplate; tinplate pretreated with a protective material such as chromium, titanium, titanate or aluminium; tin-free steel (TFS); galvanised steel, such as for example electro-galvanised steel; aluminium; aluminium alloy; and combinations thereof.
  • suitable metal substrates include, but are not limited to, food and/or beverage packaging, components used to fabricate such packaging or monobloc aerosol cans and/or tubes.
  • the food and/or beverage packaging may be a can, such as a metal can.
  • cans include, but are not limited to, two-piece cans, three-piece cans and the like.
  • monobloc aerosol cans and/or tubes include, but are not limited to, deodorant and hair spray containers.
  • Monobloc aerosol cans and/or tubes may be aluminium monobloc aerosol cans and/or tubes.
  • the substrate may be a food and/or beverage packaging or component used to fabricate such packaging.
  • the food and/or beverage can may comprise a can body and a can end.
  • the substrate may be a monobloc aerosol can and/or tube.
  • the coatings applied to the interior of metal cans also help prevent corrosion in the headspace of the cans, which is the area between the fill line of the product and the can lid; corrosion in the headspace may be problematic with food products having a high salt content. Coatings can also be applied to the exterior of metal cans.
  • the coating compositions may be applicable for use with coiled metal stock, such as the coiled metal stock from which the ends of cans are made (“can end stock”), and end caps and closures are made (“cap/closure stock”). Since coatings designed for use on can end stock and cap/closure stock may be applied prior to the piece being cut and stamped out of the coiled metal stock, they may be flexible and extensible. For example, such stock may be coated on both sides. Thereafter, the coated metal stock is punched. For can ends, the metal is then scored for the “pop-top” opening and the pop-top ring is then attached with a pin that is separately fabricated. The end is then attached to the can body by an edge rolling process. A similar procedure is done for “easy open” can ends.
  • a score substantially around the perimeter of the lid allows for easy opening or removing of the lid from the can, such as by means of a pull tab.
  • the cap/closure stock may be coated, such as by roll coating, and the cap or closure stamped out of the stock; it is possible, however, to coat the cap/closure after formation. Coatings for cans subjected to relatively stringent temperature and/or pressure requirements should also be resistant to popping, corrosion, blushing and/or blistering.
  • the substrate may be a can end, such as a metal can end.
  • the substrate may be a package coated at least in part with any of the coating compositions described herein.
  • a “package” is anything used to contain another item, such as for shipping from a point of manufacture to a consumer, and for subsequent storage by a consumer. A package will be therefore understood as something that is sealed so as to keep its contents free from deterioration until opened by a consumer. The manufacturer will often identify the length of time during which the food or beverage will be free from spoilage, which may range from several months to years. Thus, the present “package” is distinguished from a storage container or bakeware in which a consumer might make and/or store food; such a container would only maintain the freshness or integrity of the food item for a relatively short period.
  • a package according to the present disclosure can be made of metal or non-metal, for example, plastic or laminate, and be in any form.
  • An example of a suitable package is a laminate tube.
  • Another example of a suitable package is metal can.
  • the term “metal can” includes any type of metal can, container or any type of receptacle or portion thereof that is sealed by the food and/or beverage manufacturer to minimize or eliminate spoilage of the contents until such package is opened by the consumer.
  • One example of a metal can is a food can; the term “food can(s)” is used herein to refer to cans, containers or any type of receptacle or portion thereof used to hold any type of food and/or beverage.
  • metal can(s) specifically includes food cans and also specifically includes “can ends” including “E-Z open ends”, which may be stamped from can end stock and used in conjunction with the packaging of food and beverages.
  • metal cans also specifically includes metal caps and/or closures such as bottle caps, screw top caps and lids of any size, lug caps, and the like.
  • the metal cans can be used to hold other items as well, including, but not limited to, personal care products, bug spray, spray paint, and any other compound suitable for packaging in an aerosol can.
  • the cans can include “two piece cans” and “three-piece cans” as well as drawn and ironed one-piece cans; such one piece cans often find application with aerosol products.
  • Packages coated according to the present disclosure can also include plastic bottles, plastic tubes, laminates and flexible packaging, such as those made from PE, PP, PET and the like. Such packaging could hold, for example, food, toothpaste, personal care products and the like.
  • the coating compositions can be applied to the interior and/or the exterior of the package.
  • the coating compositions could also be applied as a rim coat to the bottom of the can.
  • the rim coat functions to reduce friction for improved handling during the continued fabrication and/or processing of the can.
  • the coating compositions can also be applied to caps and/or closures; such application can include, for example, a protective varnish that is applied before and/or after formation of the cap/closure and/or a pigmented enamel post applied to the cap, such as those having a scored seam at the bottom of the cap.
  • Decorated can stock can also be partially coated externally with the coating described herein, and the decorated, coated can stock used to form various metal cans.
  • Coil coatings may comprise a colorant.
  • the coating compositions may be applied to at least a portion of the substrate.
  • the coating compositions may be applied to at least a portion of an internal and/or external surface of said food and/or beverage can.
  • the coating compositions may be applied to at least a portion of an internal surface of said food and/or beverage can.
  • the coating composition may be applied as a repair coating for component parts of food and beverage cans.
  • This end component may repair coated, after fabrication, by airless spraying of the material on to the exterior of the score line.
  • Other uses as repair coatings include the coating of seams and welds, such as side seams for which the coating may be applied to the area by spraying (airless or air driven) or roller coating. Repair coating can also include protection of vulnerable areas where corrosion may be likely due to damage, these areas include flanges, rims and bottom rims where the coating may be applied by spraying, roller coating flow or dip coating.
  • Powder and like terms, as used herein, refers to materials that are in the form of solid particulates, as opposed to materials which are in the liquid form.
  • alk or “alkyl”, as used herein unless otherwise defined, relates to saturated hydrocarbon radicals being straight, branched, cyclic or polycyclic moieties or combinations thereof and contain 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 8 carbon atoms, such as 1 to 6 carbon atoms, or even 1 to 4 carbon atoms.
  • radicals may be optionally substituted with a chloro, bromo, iodo, 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 Het, wherein R 19 to R 27 each independently represent hydrogen, aryl or alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • radicals may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2- methylbutyl, pentyl, iso-amyl, hexyl, cyclohexyl, 3-methylpentyl, octyl and the like.
  • alkylene as used herein, relates to a bivalent radical alkyl group as defined above. For example, an alkyl group such as methyl which would be represented as -CHs, becomes methylene, -CH2- , when represented as an alkylene. Other alkylene groups should be understood accordingly.
  • alkenyl relates to hydrocarbon radicals having, such as up to 4, double bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and containing from 2 to 18 carbon atoms, such as 2 to 10 carbon atoms, such as from 2 to 8 carbon atoms, such as 2 to 6 carbon atoms, or even 2 to 4 carbon atoms.
  • radicals may be optionally substituted with a hydroxyl, chloro, bromo, iodo, 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, wherein R 19 to R 27 each independently represent hydrogen, aryl or alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • radicals may be independently selected from alkenyl groups include vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1 -propenyl, 2-butenyl, 2- methyl-2-butenyl, isoprenyl, farnesyl, geranyl, geranylgeranyl and the like.
  • alkynyl relates to hydrocarbon radicals having, such as up to 4, triple bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and having from 2 to 18 carbon atoms, such as 2 to 10 carbon atoms, such as from 2 to 8 carbon atoms, such as from 2 to 6 carbon atoms, or even from 2 to 4 carbon atoms.
  • radicals may be optionally substituted with a hydroxy, chloro, bromo, iodo, 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, wherein R 19 to R 27 each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • alkynyl radicals examples include ethynyl, propynyl, propargyl, butynyl, pentynyl, hexynyl and the like.
  • aryl as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.
  • radicals may be optionally substituted with a hydroxy, chloro, bromo, iodo, 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, wherein R 19 to R 27 each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsilcon groups.
  • radicals may 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- acetamidophenyl, 4-acetamidophenyl, 2-methyl-3-acetamidophenyl, 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-
  • arylene relates to a bivalent radical aryl group as defined above.
  • an aryl group such as phenyl which would be represented as -Ph, becomes phenylene, -Ph-, when represented as an arylene.
  • Other arylene groups should be understood accordingly.
  • alkyl, alkenyl, alkynyl, aryl or aralkyl in composite groups herein should be interpreted accordingly, for example the reference to alkyl in aminoalkyl or alk in alkoxyl should be interpreted as alk or alkyl above etc.
  • all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word "about", even if the term does not expressly appear.
  • the recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g.
  • 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1 .0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein. When ranges are given, any endpoints of those ranges and/or numbers within those ranges can be combined within the scope of the present disclosure.
  • the term "and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and/or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
  • a polyester copolymer was prepared as follows using the components of Table 1.
  • the material was processed the acid value was 4.00 in solution and had a viscosity of Z6+.
  • the temperature was then lowered to 160° C. (320° F.) and charge #4 was added slowly and mixed for 1 hour.
  • the reaction mixture was then filtered through a 5 micron bag.
  • the resulting number average molecular weight of the polyester was 12,063 and the weight solids was 54.81%.
  • Inventive and comparative example coating compositions were prepared by combining all of the respective materials shown in Tables 3 and 4 under mixing for 15 minutes with a mixing blade.
  • Coated panels were obtained by drawing paints over chromium pretreated aluminium panels (Henkel 702N, AA5182 Alloy) using a wire wound rod to obtain dry coating weight of approximately 6.5 to 7.5 mg/square inch (msi). All of the coated panels were then immediately placed into a three-zone, gas-fired, conveyor oven for 10 seconds and baked to a peak metal temperature of 465 °F (240.5 °C).
  • Hot Feathering A chromium pretreated aluminium panels (Henkel 702N, AA5182 Alloy) having a thickness of 0.21 mm was coated with a coating composition to give a film weight 7.0 mg/in 2 . The panel was then baked in a three zone coil oven to a peak metal temperature of 240°C. The panel was then cut into a 50.8 mm by 88.9 mm piece, with the substrate grain running perpendicular to the long length of the cut panel. The test panel coated side up was then inserted between the score tool and the anvil in a Carver press. The long edge of the panel was abutted against the guide block on the inside of the press.
  • FIG. 1 Shown in Figure 1 is a schematic of the coated panel (100) comprising the score line of the simulated tab (102).
  • the simulated tab (102) extended perpendicularly to the long length (I) of the panel.
  • the terminal points (104, 106) of the score line (which collectively form the front of the simulated tab, i.e. the portion of the tab that was first opened) were both arranged at an edge of the long length (I) of the panel.
  • the dimensions of the simulated tab (102) were: A (48.0 mm); B (11.3 mm); C (24.0 mm); D (18.00 mm); E and F area (89.4 mm 2 ); and G (10.6 mm).
  • Lengths D extended from the upper terminal point of respective length C to the left and right vertex of circles E and F, respectively.
  • Length G extended between the upper vertex of circles E and F.
  • the panel was then removed from the press and two spaced parallel cuts were formed in the panel at the front end of the simulated tab along the score line. Each cut extended inward into the panel, perpendicularly to the long length, starting from the terminal points (104 and 106) of the score line.
  • the cuts extended 6.4 mm into the panel along the respective portion of the score line and were spaced 11.3 mm apart.
  • the panel was then fully immerged into deionized water for 30 minutes at 250 °F (121 °C).
  • the panel was then removed and immediately submerged in 22°C DI water for 2 seconds.
  • the panel was then removed from the deionized water.
  • the cut portion of the simulated tab was bent 180° toward the coated face of the panel.
  • the panel was then inserted into a vice where the panel was held along the long length, with the edge from which the score line extended being held in the vice.
  • Pliers were then used to grip the cut portion of the simulated tab and then to pull the cut portion of the tab 180° across the coated face of the panel toward the opposite end of the tab at a rate of 1 second/cm. Feathering was then measured using a digital Microscope. The length of the coating that extended furthest into the tab opening was measured in mm and recorded. A lower feathering measurement indicated better adhesion.
  • Solvent Fraction is a test designed to measure the degree of cure of a coating. A four square inch disk was punched out in a hold puncher. The diskwas then weighed on a four place balance. This was the “initial weight”. Samples were then placed into racks and soaked in MEK (methyl ethyl ketone) for 10 minutes. Next, samples were removed and placed into a 400° F oven for 2 minutes, removed from the oven, cooled, and weighed again. This value was the “post bake weight”. Next, the disk was placed into Sulfuric Acid (A298-212 Technical Grade available from Fisher Scientific) for 3 minutes to strip the coating from the metal. The panel was rinsed with water to remove the coating completely. Then the panel was dried and reweighed. This was the “final weight”. The equation used to determine Solvent Fraction is:
  • Enamel rating before pack The enamel rating of the ends were measured using the Waco Enamel Rater test in which electrolyte was added to the plastic cup of Waco Enamel Rater, the can end was fitted onto the beveled end of the cup, and a vacuum applied to hold the end securely on the cup. When the cup was inverted, the electrode and can end were immersed in the electrolyte and the reading was displayed on the Enamel Rater.
  • Enamel rating after pack 47 grams of the stock solution of L-85 was added to the can followed by the addition of 308 grams of carbonated water. A 202 type seamer was then used to seam an end onto the can. The can was then placed upside down (inverted) into a 100° F.
  • the can was then removed from the incubator, opened, and then measured using the Waco Enamel Rater test in which electrolyte was added to the plastic cup of Waco Enamel Rater, the can end was fitted onto the beveled end of the cup, and a vacuum applied to hold the end securely on the cup. When the cup was inverted, the electrode and can end were immersed in the electrolyte and the reading was displayed on the Enamel Rater.
  • Pencil Hardness followsed the method ASTM D3363 - 20 Standard Test Method for Film Hardness by Pencil Test at ambient temperature.
  • Rivet Adhesion test was used to determine the degree of adhesion. The contents of a 12 ounce (355 grams) can of Budweiser which had been cooled to 1.5°C overnight was gently transferred into an empty 12 ounce (355 grams) beverage can. A CDL seamer was then used to seam the can ends onto the body of the can. The cans were pasteurized in water bath at 160°F for 30 minutes, and cooled to ambient temperature. After that, cans were placed upside down (i.e. with the can end being tested being at the bottom) in an incubator and incubated at 38°C for 24 hours. After this time, the cans were removed from the incubator and the can was punctured at the bottom to empty the liquid. The coating delamination around the rivet area will be checked. Any delamination would be considered as a fail indicating poor adhesion.
  • Polyvinyl butyral (PVB) resins with acrylic-PVA additive copolymer [354] A polymer mixture was prepared by synthesizing an acrylic polymer containing VPA in the presence of polyvinyl butyral resins with the following components listed in Table 6.
  • a polymer mixture was prepared by synthesizing an acrylic in the presence of polyvinyl butyral with the following components listed in Table 7.
  • Inventive and comparative coating compositions were prepared by combining all the respective materials shown in Table 8 by mixing for 30 minutes with a mixing blade.
  • Test panel preparation The above compositions were used to electrocoat aluminium panels by anodic electrodeposition. Panels were coated at approximately 2.0 milligrams per square inch. The coated panels were then baked in a simulated coil oven for a total of 12 seconds, with an air temperature sufficient to reach a peak metal temperature of 450° F. (232° C.) for approximately 2 seconds. The application parameters are shown in Table 9.
  • Coefficient of Friction was determined by testing an electrocoated flat panel with an Alltek digital mobility tester.
  • Rivet Adhesion and Blush Rivet Adhesion and blush test was used to determine the degree of adhesion. The contents of a 12 ounce (355 grams) can of Budweiser which had been cooled to 1 .5°C overnight was gently transferred into an empty 12 ounce (355 grams) beverage can. A CDL seamer was then used to seam the can ends onto the body of the can. The cans were pasteurized in water bath at 165°F for 30 minutes, and cooled to ambient temperature. The cans were then placed upside down (i.e. with the can end being tested being at the bottom) in an incubator and incubated at 38°C for 24 hours.
  • a polyester-graft-VPA copolymer was prepared from the components of Table 11 as follows:
  • Inventive and comparative example coating compositions were prepared by combining all of the respective materials shown in Table 12 under mixing for 15 minutes with a mixing blade.
  • Coated panels were obtained by drawing paints over chromium pretreated aluminium panels (Henkel 702N, AA5182 Alloy) using a wire wound rod to obtain dry coating weight of approximately 6.5 to 7.5 mg/square inch (msi). Coated panels were then immediately placed into a three-zone, gas-fired, conveyor oven for 10 seconds and baked to a peak metal temperature of 465 °F (240.5 °C).
  • Hot Feathering The hot feathering property of the coatings was evaluated by the following test protocol: A chromium pretreated aluminium panels (Henkel 702N, AA5182 Alloy) having a thickness of 0.21 mm was coated with a coating composition to give a film weight 7.0 mg/in 2 . The panel was then baked in a three zone coil oven to a peak metal temperature of 240°C. The panel was then cut into a 50.8 mm by 88.9 mm piece, with the substrate grain running perpendicular to the long length of the cut panel. The test panel coated side up was then inserted between the score tool and the anvil in a Carver press.
  • FIG. 1 Shown in Figure 1 is a schematic of the coated panel (100) comprising the score line of the simulated tab (102).
  • the simulated tab (102) extended perpendicularly to the long length (I) of the panel.
  • the terminal points (104, 106) of the score line (which collectively form the front of the simulated tab, i.e. the portion of the tab that was first opened) were both arranged at an edge of the long length (I) of the panel.
  • the dimensions of the simulated tab (102) were: A (48.0 mm); B (11.3 mm); C (24.0 mm); D (18.00 mm); E and F area (89.4 mm 2 ); and G (10.6 mm).
  • Lengths D extended from the upper terminal point of respective length C to the left and right vertex of circles E and F, respectively.
  • Length G extended between the upper vertex of circles E and F.
  • the panel was then removed from the press and two spaced parallel cuts were formed in the panel at the front end of the simulated tab along the score line. Each cut extended inward into the panel, perpendicularly to the long length, starting from the terminal points (104 and 106) of the score line.
  • the cuts extended 6.4 mm into the panel along the respective portion of the score line and were spaced 11.3 mm apart.
  • the panel was then fully immerged into deionized water for 30 minutes at 250 °F (121 °C).
  • the panel was then removed and immediately submerged in 22°C DI water for 2 seconds.
  • the panel was then removed from the deionized water.
  • the cut portion of the simulated tab was bent 180° toward the coated face of the panel.
  • the panel was then inserted into a vice where the panel was held along the long length, with the edge from which the score line extended being held in the vice.
  • Pliers were then used to grip the cut portion of the simulated tab and then to pull the cut portion of the tab 180° across the coated face of the panel toward the opposite end of the tab at a rate of 1 second/cm. Feathering was then measured using a digital Microscope. The length of the coating that extended furthest into the tab opening was measured in mm and recorded. A lower feathering measurement indicated better adhesion.
  • Solvent Fraction is a test designed to measure the degree of cure of a coating. A four square inch disk was punched out in a hold puncher. The disk was then weighed on a four place balance. This was the “initial weight”. Samples were then placed into racks and soaked in MEK (methyl ethyl ketone) for 10 minutes. Next, samples were removed and placed into a 400° F oven for 2 minutes, removed from the oven, cooled, and weighed again. This value was the “post bake weight”. Next, the disk was placed into Sulfuric Acid (A298-212 Technical Grade available from Fisher Scientific) for 3 minutes to strip the coating from the metal. The panel was rinsed with water to remove the coating completely. Then the panel was dried and reweighed. This was the “final weight”. The equation used to determine Solvent Fraction is:
  • Enamel rating before pack (ER) Enamel rating before pack (ER).
  • the enamel rating of the ends were measured using the Waco Enamel Rater test in which electrolyte was added to the plastic cup of Waco Enamel Rater, the can end was fitted onto the beveled end of the cup, and a vacuum applied to hold the end securely on the cup. When the cup was inverted, the electrode and can end were immersed in the electrolyte and the reading was displayed on the Enamel Rater.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

La divulgation concerne une composition de revêtement comprenant un matériau filmogène ; et un résidu d'un matériau polymérisable, le résidu comprenant un groupe fonctionnel d'acide sulfonique, de sulfate, d'acide phosphonique et/ou de phosphate. La composition de revêtement comprend un bloc de polyester-(co)polymère(B) et/ou un matériau filmogène de copolymère greffé, le bloc et/ou le copolymère greffé comprenant un (co)polymère de polyester et un (co)polymère(B), le (co)polymère(B) comprenant le résidu de matériau polymérisable comprenant un groupe fonctionnel d'acide sulfonique, de sulfate, d'acide phosphonique et/ou de phosphate ; et/ou la composition de revêtement comprenant un additif copolymère, l'additif copolymère comprenant le résidu de matériau polymérisable comprenant un groupe fonctionnel d'acide sulfonique, de sulfate, d'acide phosphonique et/ou de phosphate, l'additif copolymère pouvant être obtenu par polymérisation d'un matériau éthyléniquement insaturé avec le matériau polymérisable. La divulgation concerne également des compositions de revêtement pour l'emballage d'aliments et/ou de boissons et des articles revêtus de la composition de revêtement ainsi que des procédés de préparation et d'application de la composition de revêtement.
PCT/US2024/041401 2023-08-11 2024-08-08 Composition de revêtement Pending WO2025038370A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363519105P 2023-08-11 2023-08-11
US63/519,105 2023-08-11

Publications (1)

Publication Number Publication Date
WO2025038370A1 true WO2025038370A1 (fr) 2025-02-20

Family

ID=92503563

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/041401 Pending WO2025038370A1 (fr) 2023-08-11 2024-08-08 Composition de revêtement

Country Status (1)

Country Link
WO (1) WO2025038370A1 (fr)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793867A (en) 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US5588989A (en) 1994-11-23 1996-12-31 Ppg Industries, Inc. Zinc phosphate coating compositions containing oxime accelerators
US6417277B1 (en) * 1999-09-27 2002-07-09 Kansai Paint Co., Ltd. Coating composition
US6509408B2 (en) * 2000-05-19 2003-01-21 Akzo Nobel N.V. Aqueous cross-linkable binder composition and coating, lacquer or sealing composition comprising such a binder composition
US7749368B2 (en) 2006-12-13 2010-07-06 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated substrates
US8614286B2 (en) 2008-09-02 2013-12-24 Ppg Industries Ohio, Inc. Biomass derived radiation curable liquid coatings
US8673091B2 (en) 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US20170088745A1 (en) * 2014-03-28 2017-03-30 Valspar Sourcing, Inc. Polyester coating compositions containing polymers derived from cyclic carbonates
EP3161080A1 (fr) 2014-06-30 2017-05-03 PPG Industries Ohio, Inc. Composition de revêtement
WO2017123955A1 (fr) 2016-01-15 2017-07-20 Ppg Industries Ohio, Inc. Agents de réticulation alkyl polyurée à fonctionnalité hydroxyle
WO2018111854A1 (fr) 2016-12-12 2018-06-21 Ppg Industries Ohio, Inc. Résine polyester acrylique et composition de revêtement aqueuse la contenant
WO2020023735A1 (fr) 2018-07-25 2020-01-30 Ppg Industries Ohio, Inc. Résine de polyester acrylique et composition de revêtement aqueuse ou en poudre contenant celle-ci
WO2022165280A1 (fr) * 2021-01-29 2022-08-04 Ppg Industries Ohio, Inc. Substrat revêtu
WO2023097177A1 (fr) * 2021-11-24 2023-06-01 Ppg Industries Ohio, Inc. Copolymères à blocs (co) polymère-acrylique et compositions de revêtement les contenant

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793867A (en) 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US5588989A (en) 1994-11-23 1996-12-31 Ppg Industries, Inc. Zinc phosphate coating compositions containing oxime accelerators
US6417277B1 (en) * 1999-09-27 2002-07-09 Kansai Paint Co., Ltd. Coating composition
US6509408B2 (en) * 2000-05-19 2003-01-21 Akzo Nobel N.V. Aqueous cross-linkable binder composition and coating, lacquer or sealing composition comprising such a binder composition
US7749368B2 (en) 2006-12-13 2010-07-06 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated substrates
US8673091B2 (en) 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US8614286B2 (en) 2008-09-02 2013-12-24 Ppg Industries Ohio, Inc. Biomass derived radiation curable liquid coatings
US20170088745A1 (en) * 2014-03-28 2017-03-30 Valspar Sourcing, Inc. Polyester coating compositions containing polymers derived from cyclic carbonates
EP3161080A1 (fr) 2014-06-30 2017-05-03 PPG Industries Ohio, Inc. Composition de revêtement
US20170130086A1 (en) * 2014-06-30 2017-05-11 Irina Ponjakin A Coating Composition
WO2017123955A1 (fr) 2016-01-15 2017-07-20 Ppg Industries Ohio, Inc. Agents de réticulation alkyl polyurée à fonctionnalité hydroxyle
WO2018111854A1 (fr) 2016-12-12 2018-06-21 Ppg Industries Ohio, Inc. Résine polyester acrylique et composition de revêtement aqueuse la contenant
WO2020023735A1 (fr) 2018-07-25 2020-01-30 Ppg Industries Ohio, Inc. Résine de polyester acrylique et composition de revêtement aqueuse ou en poudre contenant celle-ci
WO2022165280A1 (fr) * 2021-01-29 2022-08-04 Ppg Industries Ohio, Inc. Substrat revêtu
WO2023097177A1 (fr) * 2021-11-24 2023-06-01 Ppg Industries Ohio, Inc. Copolymères à blocs (co) polymère-acrylique et compositions de revêtement les contenant

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"The Chemistry and Application of Phenolic Resins or Phenoplasts", vol. V, 1997, JOHN WILEY AND SONS
"The Chemistry and Applications of Amino Crosslinking agents or Aminoplast", vol. V, 1998, JOHN WILEY & SONS, pages: 21

Similar Documents

Publication Publication Date Title
US11383886B2 (en) Methods and materials for the functionalization of polymers and coatings including functionalized polymer
EP3551683B1 (fr) Résine polyester acrylique et composition de revêtement aqueuse la contenant
EP2627723B1 (fr) Composition de revêtement à base de polyester pour substrats métalliques
US12139630B2 (en) Polyhydroxyalkylamide materials for use as crosslinkers
US12344707B2 (en) Functional polyester and method of producing the same
EP4081574B1 (fr) Composition de revêtement
EP4437022A1 (fr) Copolymères à blocs (co) polymère-acrylique et compositions de revêtement les contenant
WO2025038370A1 (fr) Composition de revêtement
EP4284879A1 (fr) Composition de revêtement
CA3204739A1 (fr) Substrat revetu
WO2024243377A1 (fr) Composition de revêtement
WO2024243374A1 (fr) Composition de revêtement
CN118475628A (zh) (共)聚合物-丙烯酸嵌段共聚物和含有其的涂层组合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24759345

Country of ref document: EP

Kind code of ref document: A1