WO2010139070A1 - Fast film forming water based barrier coating - Google Patents

Fast film forming water based barrier coating Download PDF

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Publication number
WO2010139070A1
WO2010139070A1 PCT/CA2010/000847 CA2010000847W WO2010139070A1 WO 2010139070 A1 WO2010139070 A1 WO 2010139070A1 CA 2010000847 W CA2010000847 W CA 2010000847W WO 2010139070 A1 WO2010139070 A1 WO 2010139070A1
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WO
WIPO (PCT)
Prior art keywords
poly
metal ion
composition
film
fatty acid
Prior art date
Application number
PCT/CA2010/000847
Other languages
French (fr)
Inventor
François DANDENAULT
Djamel Baghdad Daidj
Serge BÉRUBÉ
Original Assignee
Retec F3 Technologies, Sec
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 Retec F3 Technologies, Sec filed Critical Retec F3 Technologies, Sec
Priority to JP2012513424A priority Critical patent/JP2012528900A/en
Priority to BRPI1011998A priority patent/BRPI1011998A2/en
Priority to EP10782873.3A priority patent/EP2438116A4/en
Priority to US13/375,792 priority patent/US20120135652A1/en
Priority to CA2764378A priority patent/CA2764378C/en
Priority to CN2010800358331A priority patent/CN102639635A/en
Publication of WO2010139070A1 publication Critical patent/WO2010139070A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • C09D125/10—Copolymers of styrene with conjugated dienes
    • 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
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31645—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to a novel composition that allows for the formation of a continuous and cohesive film which provides water resistance, grease and oil resistance release, water repellency, water vapour resistance at a very fast set speed without the need of a thermal energy, to be used as wax replacement treatment and a top coat for flexible packaging.
  • the invention also relates to packaging, containers, food wrappers, receptacles and the like formed from such coated materials.
  • the invention also relates to methods for making same.
  • the invention also relates to surface treatments in which the surface is for example metal, textile, wood, concrete and related building products.
  • Water based barrier coatings when applied to paper and paperboard contain water that has to be removed to form a continuous film.
  • the quality of the continuous film, free of defects, is very important to achieve the optimal barrier properties.
  • a drying process normally removes water.
  • the drying process is usually a thermal one (conduction, convection, radiation) in which heat is provided to the liquid to vaporize the water.
  • the drying condition is one of the most important factors that affect the coating performance. Quality problems such as bubbles, blisters, pinholes or cracks can occur with improper drying conditions.
  • the production conditions must be adapted to the type of machine, coating used and the coat weight.
  • the cost of the drying represents a major part of the process cost, and as energy costs rise, drying efficiency becomes increasingly important.
  • the invention seeks to provide a composition which with a polymer composition allows rapid formation of a dry film.
  • the invention also seeks to provide a process for providing water vapour, oil and grease resistance to a material.
  • the invention further seeks to provide the use of a composition for formation of a coating or film.
  • the invention still further seeks to provide a substrate material having a film coating.
  • the invention relates to a composition which, when mixed with a polymer composition, allows for the formation of a continuous and cohesive film.
  • the film is characterized in that it provides water, grease and oil resistance, provides a water vapour barrier and can used as wax replacement treatment and a top coat for flexible packaging, but also on other substrates. This film is formed at a very fast set speed without the need of thermal energy.
  • the invention relates to the use of i) a salt of one or more of myristic, palmitic and stearic acid; and ii) at least one of: a) polyvinyl alcohol and b) a C 9 -C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
  • the salt and the polyvinyl alcohol and/or fatty acid complex can be added individually or as part of a dispersion to the aforementioned polymer composition.
  • the invention relates to a catalytic composition
  • a catalytic composition comprising i) a metal salt of one or more of myristic, palmitic and stearic acid; and ii) at least one of: a) polyvinyl alcohol and b) a Cg - Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
  • a further aspect of the invention relates to water-based polymeric composition for film forming comprising i) a dibasic salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a Cg - Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
  • a premixture composition comprising any two of i) a dibasic salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C 9 - Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
  • the invention relates to a substrate having a surface coated with a film formed from the polymeric composition of the invention.
  • the invention further relates to a cellulose-based surface comprising a film formed from the polymeric film-forming composition of the invention.
  • the invention further relates to a metallic surface comprising a film formed from the polymeric film-forming composition of the invention.
  • the invention further relates to a textile comprising a film formed from the polymeric film-forming composition of the invention.
  • the invention further relates to glass comprising a film formed from the polymeric film-forming composition of the invention.
  • the invention further relates to a process for coating a surface comprising the use of a water-based polymeric composition without the use of thermal energy or microwave energy.
  • the invention provides, in one embodiment, a coated sheet material that is readily biodegradable, as well as recyclable and repulpable because of the classes of ingredient employed.
  • the present invention provides coated sheet material, such as cellulose-based materials including kraft paper, that is resistant to penetration by grease and oil, and that is also resistant to penetration by water moisture. Accordingly, embodiments of the present invention relate to containers and packaging for foodstuff, for frozen foods, as ovenable containers, as food wrappers, as receptacles, and as storage containers.
  • composition i) and iii) above for forming a film coating in accordance with the invention are provided.
  • the present invention relates to a water based wax-free coating which forms a film at a very fast rate without the need for added heat. It provides excellent water resistance (tack free), grease and oil resistance and good water vapour barrier properties.
  • a continuous film, free of defect, is particularly important for barrier properties.
  • Film formation in coating involves the change from liquid to solid state. This is done by the evaporation of the water and coalescence of the particles of the dispersion.
  • the polymer is initially present as discrete spheres separated by a continuous water phase. The water is removed by evaporation and by penetration into the porous substrate. As the concentration increase, the polymer particles move closer together. In this particular case, water is absorbed so fast by the substrate, that the spheres or particles are forced into ever-closer contact.
  • the spheres become crowded so tightly, that the space between them creates capillary forces. As close packing occurs, the capillary force of the water draws the spheres or particles together to form a continuous and cohesive film.
  • the ease of film formation depends on the glass transition temperature, commonly known as Tg, of the polymer, the particle size, the formulation ingredients and the temperature reached during the drying process.
  • Tg glass transition temperature
  • the present invention relates to an entirely different process wherein a salt such as calcium stearate influences the rate of film formation. Salts such as calcium stearate acts as a coalescent agent by reducing the minimum film forming temperature. Also, the salt, such as calcium stearate acts as an emulsifier and reduces the surface tension of the mixture; this allows the coating to wet the surface thoroughly and the water present in the coating is rapidly removed by penetration into the porous paper substrate.
  • the presence of the polyvinyl alcohol or the fatty acid complex of a metal ion, such as chromium, or both the polyvinyl alcohol and the fatty acid complex enhances the rate of the film formation at the same time helping to get a better film property including release, water repellency, water, water vapour, grease and oil resistance.
  • the water based barrier coating of the present invention rapidly forms a continuous and cohesive film free of defects, without the need for heat.
  • the fast set drying film formation concept of this novel water based barrier coating composition allows barrier coating technology to extend the application to the non conventional equipment such as size press coaters, spray coaters, curtain coaters and flexo where the thermal source are deficient or absent.
  • catalytic composition herein is intended to mean a pre-mixture of i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C 9 -Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
  • polymeric film-forming composition herein is intended to mean a composition comprising i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C 9 -C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
  • one aspect of the invention relates to a pre -mixture comprising of no more than two of i) a salt of one or more of myristic, palmitic and stearic acid; ii) a C9 - C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
  • the salt of one or more of myristic, palmitic and stearic acid is a typically a dibasic metal salt of these acids, and may be selected from, for instance, sodium stearate, potassium stearate, calcium stearate, zinc stearate; sodium myristate, potassium myristate, calcium myristate, or zinc myristate; sodium palmitate, potassium palmitate, calcium palmitate, and zinc palmitate.
  • the salts may be in the form of an emulsion, dispersion, or in a solvent-free state.
  • the salt of one or more of myristic, palmitic and stearic acid is a metal salt of stearic acid, namely a metal stearate. More typically, the metal stearate is a dibasic metal salt of stearic acid, such as sodium stearate, calcium stearate, lithium stearate, or zinc stearate.
  • Dispersions of calcium or zinc stearate are sold commercially under the trade marks Devflo 50LPH, Devflo 5OC and Devflo 40 RZl .
  • Commercial stearate dispersions or emulsions such as those from BASF or Rohm & Haas, are also highly suitable.
  • the C 9 -C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, is a preferred component of the catalyst composition and of the polymeric film- forming composition.
  • Quilon TM metal complexes of fatty acids have been found to be particularly suitable.
  • Other suitable release coating materials include, for example, iron(+3)-fatty acid complexes and titanium(+4)-fatty acid complexes. Good results have been achieved with trivalent metal complexes of fatty acids, such as those mentioned above.
  • the C 9 -C 18 fatty acid complex of a metal ion may be selected from a Werner complex, a trivalent metal complex of a C9-C1 8 fatty acid, a tetravalent metal complex of a Cg-Cj 8 fatty acid, such as chrome-Cg-Cig-fatty acid complexes, iron(+3)-C 9 -Ci 8 fatty acid complexes, or titanium(+4)-C 9 -Ci 8 -fatty acid complexes.
  • the C 9 -Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least +3, may, in certain embodiments have the following structure:
  • M is the metal of the metal ion
  • R' is the solvent within which the metal complex is dispersed or emulsified
  • X is a halogen, such as chlorine.
  • the metal ion is suitably chromium, such as in chromimium pentahydroxy(tetradecanoato) di-, tetradecanoato chromic chloride hydroxide, and octadecanoato chromic acid hydroxide.
  • chromimium pentahydroxy(tetradecanoato) di-, tetradecanoato chromic chloride hydroxide, and octadecanoato chromic acid hydroxide are conventionally known as QuilonTM C or C-9, QuilonTM M, and QuilonTM S.
  • QuilonTM L, QuilonTM L-1 1 and QuilonTM H are also suitable as the C 9 - Ci 8 fatty acid complex of a metal ion.
  • the Quilon complex may be Quilon C, Quilon L, Quilon M, Quilon H or Quilon S to provide specific properties.
  • QuilonTM metal complexes of fatty acids are Werner chrome complexes of a fatty acid.
  • a suitable embodiment of the invention comprises, as a C 9 - Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, a Werner complex, such as a Werner chrome complex.
  • the C 9 -C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3 may be in the form of a dispersion, suspension, emulsion, or solution in a suitable solvent.
  • the solvent may be water, an alcohol, water-miscible organic solvents, alcohol-miscible organic solvents, and combinations thereof.
  • Suitable alcohols include methanol, ethanol, proponol, isopropanol, butanol, pentanol, hexanol, heptanol, and cyclohexanol.
  • Suitable water- or alcohol-miscible organic solvents include acetonitrile, ethyl acetate, pentane, hexane, heptane and petroleum ether.
  • the polyvinyl alcohol employed alone as component (ii) or together with a C 9 -C1 8 fatty acid complex of a metal ion, as component (ii) is suitably an aqueous solution of polyvinyl alcohol, wherein the concentration, by weight of polyvinyl alcohol is typically about 10%, by weight, based on the weight of the solution.
  • the polyvinyl alcohol may be partially to fully hydrolysed.
  • Suitable polyvinyl alcohol solutions include those available under the trademark Celvol from Celanese.
  • the polyvinyl alcohol solutions may typically have a viscosity of about 28cps to about 32cps, a pH of about 5 to about 7.5, and the polyvinyl alcohol has an average weight molecular weight in the range 85,0000 to 130,000 and a number average molecular weight in the range 44,000 to 68,000.
  • An important aspect of the invention relates to the use of a salt of one or more of myristic, palmitic and stearic acid; and polyvinyl alcohol and/or a C 9 - C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3 for the preparation of a film on a surface.
  • These components can be added individually or as a mixture, such as in the form of a dispersion, suspension, emulsion, or solution.
  • An important aspect of the invention relates to a water-based mixture of a salt of one or more of myristic, palmitic and stearic acid; and at least one of: a) polyvinyl alcohol and b) a C 9 -Ci 8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
  • the catalytic composition of the invention may be in the form of a dispersion, suspension, emulsion, or solution.
  • An advantage of the present invention is that the catalytic composition of the invention may be water-based and still provide the fast-film formation on the surface.
  • the term water-based mixture is intended to mean a dispersion, suspension, emulsion, or solution wherein at least 30% (v/v) of the solvent is water, such as at least 40%, more typically at least 50%.
  • the salt of one or more of myristic, palmitic and stearic acid is selected from the group consisting of calcium stearate and zinc stearate.
  • the catalytic composition of the invention comprises calcium stearate and at least one of: a) polyvinyl alcohol and b) QuilonTM C.
  • the ratio of i) a salt of one or more of myristic, palmitic and stearic acid to ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion in the water- based catalytic composition of the invention will vary depending on the nature of the polymer composition with which the catalytic composition will eventually be mixed, and with the nature of the surface to be covered.
  • the ratio of i) a salt of one or more of myristic, palmitic and stearic acid to ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion in the water-based catalytic composition is in the range of about 5:1 to 20:1, such as from about 7:1 to 20:1, such as from about 5:1 to 15:1, more typically of about 7:1 to 15:1.
  • the catalytic composition of the invention comprises calcium stearate and at least one of: a) polyvinyl alcohol and b) QuilonTM C in a weight ratio of 5:1 to 15:1, such as about 7:1 to 15:1.
  • calcium stearate and at least one of: a) polyvinyl alcohol and b) QuilonTM C were combined in a ratio of 17 to 1.5
  • the catalytic composition of the invention may comprise a solvent-free combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a Cg-Ci 8 fatty acid complex of a metal ion.
  • the catalytic composition of the invention may comprise a combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a Cg-C is fatty acid complex of a metal ion dispersed, dissolved or suspended in the solvent within which the C 9 -C 18 fatty acid complex of a metal ion was dispersed or suspended.
  • the catalytic composition of the invention may comprise a combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a C 9 -C1 8 fatty acid complex of a metal ion, which may be dispersed, dissolved or suspended in water or an aqueous mixture, such aqueous mixture typically comprising water and the solvent or solvents within which each of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) the C 9 -Ci 8 fatty acid complex of a metal ion were dispersed, dissolved or suspended.
  • the components are present in a ratio of 15-20 to 1-2 to 1-2, such as 17 to 1.5 to 1.5.
  • the catalytic composition of the invention is combined with iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers to form a polymeric film-forming composition.
  • a further aspect of the invention relates to a polymeric film-forming composition comprising i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C 9 -C 18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, mixtures of polymers or copolymers.
  • the polymeric film-forming composition is a water-based polymeric film-forming composition.
  • the water-based polymeric film-forming composition comprises calcium or zinc stearate, at least one of: a) polyvinyl alcohol and b) a chrome-Cg-Cis-fatty acid complex such as QuilonTM C, water, and a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
  • the polymer, copolymer, or mixtures of polymers or copolymers are typically water dispersible polymers, or copolymer and are film- forming polymers or copolymers.
  • the water dispersible film forming polymers or copolymers have a Glass Transition Temperature of from about -60 to 105 °C, and are suitably selected to form a non-blocking film.
  • component (ii) is the polyvinyl alcohol, or the polyvinyl alcohol together with the C 9 -C 18 fatty acid complex of a metal ion.
  • Polymers that may be used as cross-linkable polymers resistant to water moisture in the barrier coating composition include but are not limited to: polymers and copolymers of poly(dienes) such as poly(butadiene), poly(isoprene), and poly(l-penetenylene);
  • poly(acrylics) such as poly(benzyl acrylate), poly(butyl acrylate) (s), poly(2-cyanobutyl acrylate), poly(2-ethoxyethyl acrylate), poly(ethyl acrylate), poly(2-ethylhexyl acrylate), poly(fluoromethyl acrylate), poly(5,5,6,6,7,7,7-heptafluoro-3-oxaheptyl acrylate), poly(heptafluoro-2-propyl acrylate), poly(heptyl acrylate), poly(hexyl acrylate), poly(isobornyl acrylate), poly(isopropyl acrylate), poly(3-methoxybutyl acrylate), poly(methyl acrylate), poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), and poly(p-tolyl acrylate);
  • poly(acrylamides) such as poly(acrylamide), poly(N-butylacrylamide), poly(N,N- dibutylacrylamide), poly(N-dodecylacrylamide), and poly(morpholylacrylamide);
  • poly(methacrylic acids) and poly(methacrylic acid esters) such as poly(benzyl methacrylate), poly(octyl methacrylate), poly(butyl methacrylate), poly(2-chloroethyl methacrylate), poly(2-cyanoethyl methacrylate), poly(dodecyl methacrylate), poly(2- ethylhexyl methacrylate), poly(ethyl methacrylate), poly( 1,1,1 -trifluoro-2-propyl methacrylate), poly(hexyl methacrylate), poly(2-hydroxyethyl methacrylate), poly(2- hydropropyl methacrylate), poly(isopropyl methacrylate), poly(methacrylic acid), poly(methyl methacrylate) in various forms such as, atactic, isotactic, syndiotactic, and heterotactic; and poly(propyl methacrylate);
  • poly(methacrylamides) such as poly(4-carboxy phenylmethacrylamide);
  • poly(acrylics) and poly(methacrylics) such as poly(butyl chloracrylate), poly(ethyl ethoxycarbonylmethacrylate), poly(methyl fluoroacrylate), and poly(methyl phenylacrylate);
  • poly(vinyl ethers) such as poly(butoxyethylene), poly(ethoxyethylene), poly(ethylthioethylene),
  • poly(vinyl halides) and poly(vinyl nitriles) such as poly(acrylonitrile), poly(l,l- dichloroethylene), poly(chlorotrifluoroethylene), poly(l , 1 -dichloro-2-fluoroethylene), poly(l,l-difluoroethylene), poly(methacrylonitrile), poly(vinyl chloride), and poly(vinylidene chloride);
  • polyvinyl esters such as polyvinyl acetate), poly(benzoyloxyethylene), poly(4- butyryloxybenzoyloxyethylene), poly(4-ethylbenzoyloxyethylene), poly[(trifluoroacetoxy)ethylene] , poly[(heptafluorobutyryloxy)ethylene] , poly(formyloxy ethylene), poly[(2-methoxybenzoyloxy)ethylene], poly(pivaloyloxy ethylene), and poly(propionyloxy ethylene);
  • poly(styrenes) such as, poly(4-acetylstyrene), poly[3-(4-biphenylyl)styrene], poly(4- [(2-butoxyethoxy) methyl] styrene), poly(4-butoxymethyl styrene), poly(4-butoxystyrene), poly(4-butylstyrene), poly(4-chloro-2-methylstyrene), poly(2- chlorostyrene), poly(2,4-dichlorostyrene), poly(2-ethoxymethyl styrene), poly(4- ethoxystyrene), poly(3-ethylstyrene), poly(4-fluorostyrene), poly(perfluorostyrene), poly(4-hexylstyrene), poly [4-(2-hydroxyethoxymethyl)styrene], poly [4-( 1 -hydroxy- 1- methylprop
  • poly(oxides) such as poly(ethylene oxides), poly(tetrahydrofuran), poly(oxetanes), poly(oxybutadiene), poly[oxychloromethyl)ethylene], poly(oxy-2- hydroxytrimethyleneoxy- 1 ,4-phenylenemethylene- 1 , 4-phenylene), poly(oxy-2,6- dimethoxy-l,4-phenylene), and poly(oxy-l,3-phenylene);
  • poly(carbonates) such as polycarbonate of Bisphenol A, and poly[oxycarbonyloxy-4,6- dimethyl]- 1 ,2-phenylenemethylene-3, 5 -dimethyl- 1 ,2-phenylene] ;
  • poly(esters) such as poly(ethylene terephthalate), poly[(l,2-diethoxycarbonyl)ethylene], poly[(l,2-dimethoxycarbonyl)ethylene], poly(oxy-2-butenyleneoxysebacoyl), poly [di(oxyethylene)oxyadipoyl] , polyCoxyethyleneoxycarbonyl- 1 ,4- cyclohexylenecarbonyl), poly(oxyethyleneoxyisophthaloyl), poly[di(oxyethylene)oxyoxalyl] , poly [di(oxyethylene)oxysuccinyl] , poly(oxyethyleneoxyterephthaloyl), poly(oxy- 1 ,4-phenyleneisopropyiidene- 1 ,4- phenylene oxysebacoyl), and poly(oxy-l,3-phenyleneoxyisophthaloyl);
  • poly(anhydrides) such as poly(oxycarbonyl-l,4-phenylenemethylene-l,4-phenyl enecarbonyl), and poly(oxyisophthaloyl);
  • poly(urethanes) such as poly(oxycarbonyliminohexamethyleneiminocarbonyloxydecamethylene), poly(oxyethyleneoxycarbonyliminiohexamethyleneiminocarbonyl), poly(oxyethyleneoxycarbonylimino- 1 ,4-phenylenetrimethylene- 1 ,4- phenyleneiminocarbonyl), poly(oxydodecamethyleneoxycarbonyliminodecamethyleneiminocarbonyl), and poly(oxytetramethyleneoxycarbonylimino- 1 , 4-phenylenemethylene- 1 ,A- phenyleneiminocarbonyl);
  • poly(siloxanes) such as, poly(dimethylsiloxane), poly[oxy(methyl)phenylsilylene], and poly(oxydiphenylsilylene-l ,3-phenylene);
  • poly(sulfones) and poly(sulfonamides) such as poly[oxycarbonyl di(oxy-l,4- phenylene)sulfonyl- 1 , 4-phenyleneoxy- 1 ,4-phenylene] , poly [oxy- 1 ,4- phenylenesulfinyl- 1 ,4-phenyleneoxy- 1 , 4-phenylenecarbonyl- 1 ,4-phenylene), poly(oxy- 1 ,4-phenylenesulfonyl- 1 ,4-phenylene), and poly(sulfonyl- 1,3- cyclohexylene);
  • poly(amides) such as nylon-6, nylon-6,6, nylon-3, nylon-4,6, nylon-5,6, nylon-6,3, nylon-6,2, nylon-6, 12, and nylon- 12;
  • poly(imines) such as poly(acetyliminoethylene), and poly(valeryl iminoethylene);
  • poly(benzimidazoles) such as poly(2,6-benzimidazolediyl-6,2- benzimidazolediyloctamethylene) ;
  • carbohydrates such as amylose triacetate, cellulose triacetate, cellulose tridecanoate, ethyl cellulose, and methylcellulose;
  • the water dispersible film-forming are typically selected from the group comprising:
  • the present invention relates to a novel composition that allows for the formation of a continuous and cohesive film which provides water resistance, grease and oil resistance, and water vapour barrier properties at a very fast set speed without the need of a thermal energy and which can be used as wax replacement treatment and a top coat for flexible packaging.
  • the absence of the need to apply thermal energy has dramatic advantages from an industrial, commercial, plant manufacturing and economic stand point.
  • the ability to provide a continuous and cohesive film which provides a water resistance, grease and oil resistance, and water vapour barrier properties without the presence of wax has dramatic environmental implications, as well as economic considerations given the volatile costs of petroleum based products.
  • the term absence of thermal energy, or the need for added thermal energy is intended to mean that a heater, oven or other direct heating device is not required in the film-forming process of the invention.
  • the process occurs without direct heating. Otherwise stated, the film-forming process occurs at a temperature from about 0 to 5O 0 C, typically from about 10 to 45°C, such as 15 to 40 0 C, typically at ambient temperature between 15 to 35 0 C.
  • the catalytic composition allows for the water-based polymeric composition to form a film at a first rate without added heat.
  • the catalytic composition allows for the water-based polymeric composition to form a film without added heat with the film-formation in less than one minute from application of the composition to the surface.
  • the catalytic composition allows for the water-based polymeric composition to form a film without added heat and without the use of wax.
  • wax free composition, free of wax, without wax is intended to mean a polymeric composition, and resultant film with less than 0.1% wax, typically with 0% wax.
  • the film-forming polymeric composition of the invention may optionally comprise a tackifier resin, such as an aqueous dispersion of glycerol ester of hydrogenated rosin.
  • a tackifier resin such as an aqueous dispersion of glycerol ester of hydrogenated rosin.
  • the film-forming polymeric composition of the invention may optionally comprise a filler selected from the group consisting of delaminated clays, kaolin, mica, talc or a mixture, silicate, calcium silicate, calcium carbonate, aluminium hydrate, and mixtures thereof.
  • a filler selected from the group consisting of delaminated clays, kaolin, mica, talc or a mixture, silicate, calcium silicate, calcium carbonate, aluminium hydrate, and mixtures thereof.
  • the film-forming polymeric composition of the invention may optionally comprise an internal sizing agent, for example an alkyl ketone dimer (AKD) and or an alkyl succinic anhydride (ASA).
  • an internal sizing agent for example an alkyl ketone dimer (AKD) and or an alkyl succinic anhydride (ASA).
  • the film-forming polymeric composition of the invention may optionally comprise a dispersing agent, a thickener agent, a defoaming agent, a slip agent, an antiskid agent, rheology modifiers, pigments, susceptor materials, crosslinking agents, catalysts, flame retardants, biocides, and wetting agent.
  • Pigment may be added to the film-forming composition to give the surface of the coated substrate or sheet material a desired appearance. For example, it may be desired that a food-contacting surface of the coated sheet material be a white color. In the event brown kraft paper is used as the substrate sheet material, titanium dioxide may be added to the barrier coating composition to make it white and to make the food-contacting surface of the sheet material white when the barrier coating composition is applied. Pigments such as TI-PURE® 900, a titanium dioxide pigment made by DuPont, are suitable pigments for the barrier coating. Other pigments or dispersions may be suitable so long as they do not significantly degrade the performance of the barrier coating composition.
  • a dispersing agent may be added to the film-forming composition to help disperse and suspend any component, including fillers and pigment particles, in the composition before application, and to stabilize the suspension.
  • Any of a variety of dispersing agents may be used.
  • dispersing agents such as tetra sodium pyrophosphate ("TSPP") and sodium hexa meta phosphate are suitable for this purpose.
  • TSPP tetra sodium pyrophosphate
  • the fast drying film formation barrier coatings composition suitably comprises, in weight % to a total of 100%, the following:
  • the film-forming composition of the invention is applied, without the need for added thermal energy, in the form of a solution, dispersion, emulsion, suspension, or in a solvent-free form to the surface of a material for film-formation.
  • the material may be cellulose-based, metallic, textile, cement, sand, stone or glass.
  • Cellulose-based materials include paper, card, wood of all sorts, including paperboard, kraft paper. Some of the numerous uses include use in frozen-foods, food packaging, paper for baking, corrugated paperboard, cardboard boxes, wrapping materials for consumable and non-consumable goods, such as hamburgers and sandwiches, such as in fast-food outlets.
  • Metallic surfaces such as pans, pots and baking trays, each comprising a film prepared from a film-forming composition of the invention, are also anticipated.
  • Furniture and wood- based building materials each comprising a film prepared from a film-forming composition of the invention, are also anticipated.
  • cement, outdoor tiling, pavement and the like each comprising a film prepared from a film- forming composition of the invention, are also anticipated.
  • component ii) hereinbefore namely, the polyvinyl alcohol and/or C 9 -C1 8 fatty acid complex of a metal ion
  • acceptable film forming compositions are provided by components i) and iii) described hereinbefore, in accordance with the invention, especially when component i) is in a relatively high concentration.
  • these compositions will improve 20 to 40% by weight of component i) and 80 to 60% of component iii) to a total of 100%.
  • novel water based barrier coating compositions are express in weight % to a total of 100%.
  • Styronal 4606X 80.0% (trade mark for an aqueous styrene-butadiene dispersion)
  • Polyplate P 10.0 % Polygloss 90: 19.6%
  • PVOH as an aqueous solution at 10 % ... 16.8 to 1.8 %
  • PVOH as an aqueous solution at 10 wt.% ... 6.0 to 10.0 % Stearate Devflo 50C ... 54.0 to 10.0 %

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Abstract

The invention relates to a composition which, when mixed with a polymer composition, allows for the formation of a continuous and cohesive film. The film is characterized in that it provides water, grease and oil resistance, provides a water vapour barrier and can used as wax replacement treatment and a top coat for flexible packaging, but also on other substrates. This film is formed at a very fast set speed without the need of thermal energy. The composition contains i) a salt of one or more of myristic, palmitic and stearic acid; ii) polyvinyl alcohol, and optionally also iii) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3. The invention also provides processes and coated substrates.

Description

FAST FILM FORMING WATER BASED BARRIER COATING
TECHNICAL FIELD
The present invention relates to a novel composition that allows for the formation of a continuous and cohesive film which provides water resistance, grease and oil resistance release, water repellency, water vapour resistance at a very fast set speed without the need of a thermal energy, to be used as wax replacement treatment and a top coat for flexible packaging. The invention also relates to packaging, containers, food wrappers, receptacles and the like formed from such coated materials. The invention also relates to methods for making same. The invention also relates to surface treatments in which the surface is for example metal, textile, wood, concrete and related building products.
BACKGROUND ART
Water based barrier coatings when applied to paper and paperboard contain water that has to be removed to form a continuous film. The quality of the continuous film, free of defects, is very important to achieve the optimal barrier properties.
A drying process normally removes water. The drying process is usually a thermal one (conduction, convection, radiation) in which heat is provided to the liquid to vaporize the water.
The drying condition is one of the most important factors that affect the coating performance. Quality problems such as bubbles, blisters, pinholes or cracks can occur with improper drying conditions. The production conditions must be adapted to the type of machine, coating used and the coat weight.
The cost of the drying represents a major part of the process cost, and as energy costs rise, drying efficiency becomes increasingly important.
Thus, in a time of concern over energy environment and petroleum resources, it would be beneficial to be able to coat paper using water based barrier coating without the need of heat or dryer while still having a high rate of speed of coating.
DISCLOSURE OF THE INVENTION
The invention seeks to provide a composition which with a polymer composition allows rapid formation of a dry film.
The invention also seeks to provide a process for providing water vapour, oil and grease resistance to a material.
The invention further seeks to provide the use of a composition for formation of a coating or film.
The invention still further seeks to provide a substrate material having a film coating.
In one aspect the invention relates to a composition which, when mixed with a polymer composition, allows for the formation of a continuous and cohesive film. The film is characterized in that it provides water, grease and oil resistance, provides a water vapour barrier and can used as wax replacement treatment and a top coat for flexible packaging, but also on other substrates. This film is formed at a very fast set speed without the need of thermal energy.
In another aspect the invention relates to the use of i) a salt of one or more of myristic, palmitic and stearic acid; and ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
The salt and the polyvinyl alcohol and/or fatty acid complex can be added individually or as part of a dispersion to the aforementioned polymer composition.
Accordingly, in another aspect the invention relates to a catalytic composition comprising i) a metal salt of one or more of myristic, palmitic and stearic acid; and ii) at least one of: a) polyvinyl alcohol and b) a Cg - Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
A further aspect of the invention relates to water-based polymeric composition for film forming comprising i) a dibasic salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a Cg - Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
Another aspect of the invention relates to a premixture composition comprising any two of i) a dibasic salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C9 - Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
In yet another aspect the invention relates to a substrate having a surface coated with a film formed from the polymeric composition of the invention.
The invention further relates to a cellulose-based surface comprising a film formed from the polymeric film-forming composition of the invention. The invention further relates to a metallic surface comprising a film formed from the polymeric film-forming composition of the invention. The invention further relates to a textile comprising a film formed from the polymeric film-forming composition of the invention. The invention further relates to glass comprising a film formed from the polymeric film-forming composition of the invention.
The invention further relates to a process for coating a surface comprising the use of a water-based polymeric composition without the use of thermal energy or microwave energy.
The invention provides, in one embodiment, a coated sheet material that is readily biodegradable, as well as recyclable and repulpable because of the classes of ingredient employed. The present invention provides coated sheet material, such as cellulose-based materials including kraft paper, that is resistant to penetration by grease and oil, and that is also resistant to penetration by water moisture. Accordingly, embodiments of the present invention relate to containers and packaging for foodstuff, for frozen foods, as ovenable containers, as food wrappers, as receptacles, and as storage containers.
In still another aspect of the invention there is provided a composition i) and iii) above for forming a film coating in accordance with the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to a water based wax-free coating which forms a film at a very fast rate without the need for added heat. It provides excellent water resistance (tack free), grease and oil resistance and good water vapour barrier properties.
The success of functional coatings generally depends on having a uniform coating. A continuous film, free of defect, is particularly important for barrier properties. Film formation in coating involves the change from liquid to solid state. This is done by the evaporation of the water and coalescence of the particles of the dispersion. The polymer is initially present as discrete spheres separated by a continuous water phase. The water is removed by evaporation and by penetration into the porous substrate. As the concentration increase, the polymer particles move closer together. In this particular case, water is absorbed so fast by the substrate, that the spheres or particles are forced into ever-closer contact.
Eventually, the spheres become crowded so tightly, that the space between them creates capillary forces. As close packing occurs, the capillary force of the water draws the spheres or particles together to form a continuous and cohesive film.
The ease of film formation depends on the glass transition temperature, commonly known as Tg, of the polymer, the particle size, the formulation ingredients and the temperature reached during the drying process. The present invention relates to an entirely different process wherein a salt such as calcium stearate influences the rate of film formation. Salts such as calcium stearate acts as a coalescent agent by reducing the minimum film forming temperature. Also, the salt, such as calcium stearate acts as an emulsifier and reduces the surface tension of the mixture; this allows the coating to wet the surface thoroughly and the water present in the coating is rapidly removed by penetration into the porous paper substrate.
The presence of the polyvinyl alcohol or the fatty acid complex of a metal ion, such as chromium, or both the polyvinyl alcohol and the fatty acid complex, enhances the rate of the film formation at the same time helping to get a better film property including release, water repellency, water, water vapour, grease and oil resistance.
Therefore the water based barrier coating of the present invention rapidly forms a continuous and cohesive film free of defects, without the need for heat. The fast set drying film formation concept of this novel water based barrier coating composition allows barrier coating technology to extend the application to the non conventional equipment such as size press coaters, spray coaters, curtain coaters and flexo where the thermal source are deficient or absent.
The term catalytic composition herein is intended to mean a pre-mixture of i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
The term polymeric film-forming composition herein is intended to mean a composition comprising i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
It has been found that air exposure to the polymeric film-forming composition of the invention leads to film formation from the composition, such as a film forming on its surface. Accordingly, one aspect of the invention relates to a pre -mixture comprising of no more than two of i) a salt of one or more of myristic, palmitic and stearic acid; ii) a C9 - C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
The salt of one or more of myristic, palmitic and stearic acid is a typically a dibasic metal salt of these acids, and may be selected from, for instance, sodium stearate, potassium stearate, calcium stearate, zinc stearate; sodium myristate, potassium myristate, calcium myristate, or zinc myristate; sodium palmitate, potassium palmitate, calcium palmitate, and zinc palmitate. The salts may be in the form of an emulsion, dispersion, or in a solvent-free state.
In a suitable embodiment, the salt of one or more of myristic, palmitic and stearic acid is a metal salt of stearic acid, namely a metal stearate. More typically, the metal stearate is a dibasic metal salt of stearic acid, such as sodium stearate, calcium stearate, lithium stearate, or zinc stearate.
Dispersions of calcium or zinc stearate are sold commercially under the trade marks Devflo 50LPH, Devflo 5OC and Devflo 40 RZl . Commercial stearate dispersions or emulsions, such as those from BASF or Rohm & Haas, are also highly suitable.
The C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, is a preferred component of the catalyst composition and of the polymeric film- forming composition. Quilon ™ metal complexes of fatty acids have been found to be particularly suitable. Other suitable release coating materials include, for example, iron(+3)-fatty acid complexes and titanium(+4)-fatty acid complexes. Good results have been achieved with trivalent metal complexes of fatty acids, such as those mentioned above. Accordingly, the C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, may be selected from a Werner complex, a trivalent metal complex of a C9-C18 fatty acid, a tetravalent metal complex of a Cg-Cj8 fatty acid, such as chrome-Cg-Cig-fatty acid complexes, iron(+3)-C9-Ci8 fatty acid complexes, or titanium(+4)-C9-Ci8-fatty acid complexes.
Without being bound by a particular theory, the C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least +3, may, in certain embodiments have the following structure:
Figure imgf000008_0001
wherein M is the metal of the metal ion, R' is the solvent within which the metal complex is dispersed or emulsified, and X is a halogen, such as chlorine.
The metal ion is suitably chromium, such as in chromimium pentahydroxy(tetradecanoato) di-, tetradecanoato chromic chloride hydroxide, and octadecanoato chromic acid hydroxide. These are conventionally known as Quilon™ C or C-9, Quilon™ M, and Quilon™ S. Also suitable as the C9 - Ci8 fatty acid complex of a metal ion are Quilon™ L, Quilon™ L-1 1 and Quilon™ H, including mixtures of any of the foregoing.
Thus, the Quilon complex may be Quilon C, Quilon L, Quilon M, Quilon H or Quilon S to provide specific properties.
Quilon™ metal complexes of fatty acids are Werner chrome complexes of a fatty acid. A suitable embodiment of the invention comprises, as a C9 - Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, a Werner complex, such as a Werner chrome complex. C]I-CiS fatty acid complexes of a metal ion having an oxidation stable of at least 3, such as chromium, have been found expressly suitable.
The C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3 may be in the form of a dispersion, suspension, emulsion, or solution in a suitable solvent. The solvent may be water, an alcohol, water-miscible organic solvents, alcohol-miscible organic solvents, and combinations thereof. Suitable alcohols include methanol, ethanol, proponol, isopropanol, butanol, pentanol, hexanol, heptanol, and cyclohexanol. Suitable water- or alcohol-miscible organic solvents include acetonitrile, ethyl acetate, pentane, hexane, heptane and petroleum ether.
The polyvinyl alcohol employed alone as component (ii) or together with a C9-C18 fatty acid complex of a metal ion, as component (ii) is suitably an aqueous solution of polyvinyl alcohol, wherein the concentration, by weight of polyvinyl alcohol is typically about 10%, by weight, based on the weight of the solution. The polyvinyl alcohol may be partially to fully hydrolysed. Suitable polyvinyl alcohol solutions include those available under the trademark Celvol from Celanese.
The polyvinyl alcohol solutions may typically have a viscosity of about 28cps to about 32cps, a pH of about 5 to about 7.5, and the polyvinyl alcohol has an average weight molecular weight in the range 85,0000 to 130,000 and a number average molecular weight in the range 44,000 to 68,000.
An important aspect of the invention relates to the use of a salt of one or more of myristic, palmitic and stearic acid; and polyvinyl alcohol and/or a C9 - C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3 for the preparation of a film on a surface. These components can be added individually or as a mixture, such as in the form of a dispersion, suspension, emulsion, or solution.
An important aspect of the invention relates to a water-based mixture of a salt of one or more of myristic, palmitic and stearic acid; and at least one of: a) polyvinyl alcohol and b) a C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3. The catalytic composition of the invention may be in the form of a dispersion, suspension, emulsion, or solution. An advantage of the present invention is that the catalytic composition of the invention may be water-based and still provide the fast-film formation on the surface. The term water-based mixture is intended to mean a dispersion, suspension, emulsion, or solution wherein at least 30% (v/v) of the solvent is water, such as at least 40%, more typically at least 50%.
In a highly suitable embodiment of the water-based mixture of a salt of one or more of myristic, palmitic and stearic acid; and at least one of: a) polyvinyl alcohol and b) a C9- C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, the salt of one or more of myristic, palmitic and stearic acid is selected from the group consisting of calcium stearate and zinc stearate.
In a further highly suitable embodiment of the water-based mixture of a salt of one or more of myristic, palmitic and stearic acid; and at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, the C9-C18 fatty acid complex of a metal ion is a chrome- C9-C18 fatty acid complex, such as one having the chemical composition of Quilon™ C. In a highly suitable embodiment, the catalytic composition of the invention comprises calcium stearate and at least one of: a) polyvinyl alcohol and b) Quilon™ C.
The ratio of i) a salt of one or more of myristic, palmitic and stearic acid to ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion in the water- based catalytic composition of the invention will vary depending on the nature of the polymer composition with which the catalytic composition will eventually be mixed, and with the nature of the surface to be covered. Typically, the ratio of i) a salt of one or more of myristic, palmitic and stearic acid to ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion in the water-based catalytic composition, is in the range of about 5:1 to 20:1, such as from about 7:1 to 20:1, such as from about 5:1 to 15:1, more typically of about 7:1 to 15:1.
In a highly suitable embodiment of the invention, the catalytic composition of the invention comprises calcium stearate and at least one of: a) polyvinyl alcohol and b) Quilon™ C in a weight ratio of 5:1 to 15:1, such as about 7:1 to 15:1. In one embodiment calcium stearate and at least one of: a) polyvinyl alcohol and b) Quilon™ C were combined in a ratio of 17 to 1.5
The catalytic composition of the invention may comprise a solvent-free combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a Cg-Ci8 fatty acid complex of a metal ion. Alternatively, the catalytic composition of the invention may comprise a combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a Cg-C is fatty acid complex of a metal ion dispersed, dissolved or suspended in the solvent within which the C9-C18 fatty acid complex of a metal ion was dispersed or suspended. In a further alternative, the catalytic composition of the invention may comprise a combination of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion, which may be dispersed, dissolved or suspended in water or an aqueous mixture, such aqueous mixture typically comprising water and the solvent or solvents within which each of i) the salt of one or more of myristic, palmitic and stearic acid and ii) at least one of: a) polyvinyl alcohol and b) the C9-Ci8 fatty acid complex of a metal ion were dispersed, dissolved or suspended.
In an embodiment of the invention comprising i) calcium or zinc stearate and ii) at least one of: a) polyvinyl alcohol and b) a chrome-C9-Cis-fatty acid complex such as Quilon™ C, and water, the components are present in a ratio of 15-20 to 1-2 to 1-2, such as 17 to 1.5 to 1.5.
The catalytic composition of the invention is combined with iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers to form a polymeric film-forming composition. Accordingly, a further aspect of the invention relates to a polymeric film-forming composition comprising i) a salt of one or more of myristic, palmitic and stearic acid; ii) at least one of: a) polyvinyl alcohol and b) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, mixtures of polymers or copolymers. In a typical embodiment, the polymeric film-forming composition is a water-based polymeric film-forming composition. In a highly typical embodiment, the water-based polymeric film-forming composition comprises calcium or zinc stearate, at least one of: a) polyvinyl alcohol and b) a chrome-Cg-Cis-fatty acid complex such as Quilon™ C, water, and a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers.
The polymer, copolymer, or mixtures of polymers or copolymers, are typically water dispersible polymers, or copolymer and are film- forming polymers or copolymers. In the preferred embodiment, the water dispersible film forming polymers or copolymers have a Glass Transition Temperature of from about -60 to 105 °C, and are suitably selected to form a non-blocking film.
In especially preferred embodiments of the invention, component (ii) is the polyvinyl alcohol, or the polyvinyl alcohol together with the C9-C18 fatty acid complex of a metal ion.
Polymers that may be used as cross-linkable polymers resistant to water moisture in the barrier coating composition include but are not limited to: polymers and copolymers of poly(dienes) such as poly(butadiene), poly(isoprene), and poly(l-penetenylene);
• poly(acrylics) such as poly(benzyl acrylate), poly(butyl acrylate) (s), poly(2-cyanobutyl acrylate), poly(2-ethoxyethyl acrylate), poly(ethyl acrylate), poly(2-ethylhexyl acrylate), poly(fluoromethyl acrylate), poly(5,5,6,6,7,7,7-heptafluoro-3-oxaheptyl acrylate), poly(heptafluoro-2-propyl acrylate), poly(heptyl acrylate), poly(hexyl acrylate), poly(isobornyl acrylate), poly(isopropyl acrylate), poly(3-methoxybutyl acrylate), poly(methyl acrylate), poly(nonyl acrylate), poly(octyl acrylate), poly(propyl acrylate), and poly(p-tolyl acrylate);
• polyvinylacrylates, fluorocarbons and fluoropolymers;
• poly(acrylamides) such as poly(acrylamide), poly(N-butylacrylamide), poly(N,N- dibutylacrylamide), poly(N-dodecylacrylamide), and poly(morpholylacrylamide);
• poly(methacrylic acids) and poly(methacrylic acid esters) such as poly(benzyl methacrylate), poly(octyl methacrylate), poly(butyl methacrylate), poly(2-chloroethyl methacrylate), poly(2-cyanoethyl methacrylate), poly(dodecyl methacrylate), poly(2- ethylhexyl methacrylate), poly(ethyl methacrylate), poly( 1,1,1 -trifluoro-2-propyl methacrylate), poly(hexyl methacrylate), poly(2-hydroxyethyl methacrylate), poly(2- hydropropyl methacrylate), poly(isopropyl methacrylate), poly(methacrylic acid), poly(methyl methacrylate) in various forms such as, atactic, isotactic, syndiotactic, and heterotactic; and poly(propyl methacrylate);
• poly(methacrylamides) such as poly(4-carboxy phenylmethacrylamide);
• other alpha-and beta-substituted poly(acrylics) and poly(methacrylics) such as poly(butyl chloracrylate), poly(ethyl ethoxycarbonylmethacrylate), poly(methyl fluoroacrylate), and poly(methyl phenylacrylate);
• poly(vinyl ethers) such as poly(butoxyethylene), poly(ethoxyethylene), poly(ethylthioethylene),
• (dodecafluorobutoxyethylene), poly poly(2,2,2-trifluoroethoxytrifluoroethylene), poly(hexyloxy ethylene), poly(methoxy ethylene), and poly(2-methoxypropylene);
• poly(vinyl halides) and poly(vinyl nitriles) such as poly(acrylonitrile), poly(l,l- dichloroethylene), poly(chlorotrifluoroethylene), poly(l , 1 -dichloro-2-fluoroethylene), poly(l,l-difluoroethylene), poly(methacrylonitrile), poly(vinyl chloride), and poly(vinylidene chloride);
• polyvinyl esters) such as polyvinyl acetate), poly(benzoyloxyethylene), poly(4- butyryloxybenzoyloxyethylene), poly(4-ethylbenzoyloxyethylene), poly[(trifluoroacetoxy)ethylene] , poly[(heptafluorobutyryloxy)ethylene] , poly(formyloxy ethylene), poly[(2-methoxybenzoyloxy)ethylene], poly(pivaloyloxy ethylene), and poly(propionyloxy ethylene);
• poly(styrenes) such as, poly(4-acetylstyrene), poly[3-(4-biphenylyl)styrene], poly(4- [(2-butoxyethoxy) methyl] styrene), poly(4-butoxymethyl styrene), poly(4- butoxystyrene), poly(4-butylstyrene), poly(4-chloro-2-methylstyrene), poly(2- chlorostyrene), poly(2,4-dichlorostyrene), poly(2-ethoxymethyl styrene), poly(4- ethoxystyrene), poly(3-ethylstyrene), poly(4-fluorostyrene), poly(perfluorostyrene), poly(4-hexylstyrene), poly [4-(2-hydroxyethoxymethyl)styrene], poly [4-( 1 -hydroxy- 1- methylpropyl)styrene], poly(2-methoxymethylstyrene), poly(2-methoxystyrene), poly(alpha-methylstyrene), poly(2-methylstyrene), poly(4-methoxystyrene), poly(4- octanoylstyrene), poly(4-phenoxystyrene), poly(4-phenylstyrene), poly(4- propoxy styrene), and poly(styrene);
• poly(oxides) such as poly(ethylene oxides), poly(tetrahydrofuran), poly(oxetanes), poly(oxybutadiene), poly[oxychloromethyl)ethylene], poly(oxy-2- hydroxytrimethyleneoxy- 1 ,4-phenylenemethylene- 1 , 4-phenylene), poly(oxy-2,6- dimethoxy-l,4-phenylene), and poly(oxy-l,3-phenylene);
• poly(carbonates) such as polycarbonate of Bisphenol A, and poly[oxycarbonyloxy-4,6- dimethyl]- 1 ,2-phenylenemethylene-3, 5 -dimethyl- 1 ,2-phenylene] ;
• poly(esters) such as poly(ethylene terephthalate), poly[(l,2-diethoxycarbonyl)ethylene], poly[(l,2-dimethoxycarbonyl)ethylene], poly(oxy-2-butenyleneoxysebacoyl), poly [di(oxyethylene)oxyadipoyl] , polyCoxyethyleneoxycarbonyl- 1 ,4- cyclohexylenecarbonyl), poly(oxyethyleneoxyisophthaloyl), poly[di(oxyethylene)oxyoxalyl] , poly [di(oxyethylene)oxysuccinyl] , poly(oxyethyleneoxyterephthaloyl), poly(oxy- 1 ,4-phenyleneisopropyiidene- 1 ,4- phenylene oxysebacoyl), and poly(oxy-l,3-phenyleneoxyisophthaloyl);
• poly(anhydrides) such as poly(oxycarbonyl-l,4-phenylenemethylene-l,4-phenyl enecarbonyl), and poly(oxyisophthaloyl);
• poly(urethanes) such as poly(oxycarbonyliminohexamethyleneiminocarbonyloxydecamethylene), poly(oxyethyleneoxycarbonyliminiohexamethyleneiminocarbonyl), poly(oxyethyleneoxycarbonylimino- 1 ,4-phenylenetrimethylene- 1 ,4- phenyleneiminocarbonyl), poly(oxydodecamethyleneoxycarbonyliminodecamethyleneiminocarbonyl), and poly(oxytetramethyleneoxycarbonylimino- 1 , 4-phenylenemethylene- 1 ,A- phenyleneiminocarbonyl);
• poly(siloxanes) such as, poly(dimethylsiloxane), poly[oxy(methyl)phenylsilylene], and poly(oxydiphenylsilylene-l ,3-phenylene);
• poly(sulfones) and poly(sulfonamides) such as poly[oxycarbonyl di(oxy-l,4- phenylene)sulfonyl- 1 , 4-phenyleneoxy- 1 ,4-phenylene] , poly [oxy- 1 ,4- phenylenesulfinyl- 1 ,4-phenyleneoxy- 1 , 4-phenylenecarbonyl- 1 ,4-phenylene), poly(oxy- 1 ,4-phenylenesulfonyl- 1 ,4-phenylene), and poly(sulfonyl- 1,3- cyclohexylene);
• poly(amides) such as nylon-6, nylon-6,6, nylon-3, nylon-4,6, nylon-5,6, nylon-6,3, nylon-6,2, nylon-6, 12, and nylon- 12;
• poly(imines) such as poly(acetyliminoethylene), and poly(valeryl iminoethylene);
• poly(benzimidazoles) such as poly(2,6-benzimidazolediyl-6,2- benzimidazolediyloctamethylene) ;
• carbohydrates such as amylose triacetate, cellulose triacetate, cellulose tridecanoate, ethyl cellulose, and methylcellulose;
• and polymer mixtures and copolymers thereof such as poly(acrylonitrile-co-styrene) with poly(e-caprolactone), or poly(ethyl methacrylate), or poly(methyl methacrylate);
• Poly (acrylonitrile-co-vinylidene chloride) with poly(hexamethylene terephthalate);
• Poly (allyl alcohol-co-styrene) with poly(butylene adipate), or poly(butylene sebacate); poly(n-amyl methacrylate) with poly(vinyl chloride);
• bisphenol A polycarbonate with poly(e-caprolactone), or poly(ethylene adipate), or poly(ethylene terephthalate), or novolac resin;
• poly(butadiene) with poly(isoprene); • poly(butadiene-co-styrene) with glycerol ester of hydrogenated rosin;
• poly(butyl acrylate) with poly(chlorinated ethylene), or poly(vinyl chloride);
• poly(butyl acrylate-co-methyl methacrylate) with polyvinyl chloride);
• poly(butyl methacrylate) with poly(vinyl chloride);
• poly(butylene terephthalate) with poly(ethylene terephthalate), or poly(vinyl acetate-co- vinylidene chloride);
• poly(e-caprolactone) with poly(chlorostyrene), or poly(vinyl acetate-co-vinylidene chloride);
• cellulose acetate with poly(vinylidene chloride-co-styrene);
• cellulose acetate-butyrate with poly(ethylene-co-vinyl acetate);
• poly(chlorinated ethylene) with poly(methyl methacrylate);
• poly(chlorinated vinyl chloride) with poly(n-butyl methacrylate), or poly(ethyl methacrylate), or poly(valerolactone);
• poly(chloroprene) with poly(ethylene-co-methyl acrylate);
• poly(2,6-dimethyl-l,4-phenylene oxide) with poly(a-methylstyrene-co-styrene styrene), or poly(styrene);
• poly(ethyl acrylate) with poly(vinyl chloride-co-vinylidene chloride), or polyvinyl chloride);
• poly(ethyl methacrylate) with poly(vinyl chloride);
• poly(ethylene oxide) with poly(methyl methacrylate);
• poly( styrene) with poly(vinyl methyl ether); and
• poly(valerolactone) with poly(vinyl acetate-co-vinylidene chloride). The water dispersible film-forming are typically selected from the group comprising:
- Styrene butadiene copolymers, typically in a dispersion;
- Modified styrene butadiene copolymers, typically in a dispersion;
- Styrene / acrylate copolymers, typically in a dispersion: - Carboxylated polystyrene, typically in a dispersion:
- Acrylic / polyacrylic polymers, typically in an emulsion
- Polyvinyl Acetate;
- Polypolyvinyl alcohol,
- Polyvinylacetate-ethylene, - Polyvinyl acrylic;
- Soy protein polymer;
- Corn Zein (protein) or starch, typically in a dispersion;
- Polyolefin dispersion as modified propylene-based dispersion;
- Rosin ester dispersions, and - Poly vinylidene chloride.
The present invention relates to a novel composition that allows for the formation of a continuous and cohesive film which provides water resistance, grease and oil resistance, and water vapour barrier properties at a very fast set speed without the need of a thermal energy and which can be used as wax replacement treatment and a top coat for flexible packaging. The absence of the need to apply thermal energy has dramatic advantages from an industrial, commercial, plant manufacturing and economic stand point. The ability to provide a continuous and cohesive film which provides a water resistance, grease and oil resistance, and water vapour barrier properties without the presence of wax has dramatic environmental implications, as well as economic considerations given the volatile costs of petroleum based products.
The term absence of thermal energy, or the need for added thermal energy is intended to mean that a heater, oven or other direct heating device is not required in the film-forming process of the invention. The process occurs without direct heating. Otherwise stated, the film-forming process occurs at a temperature from about 0 to 5O0C, typically from about 10 to 45°C, such as 15 to 400C, typically at ambient temperature between 15 to 35 0C.
The catalytic composition allows for the water-based polymeric composition to form a film at a first rate without added heat. The catalytic composition allows for the water- based polymeric composition to form a film without added heat with the film-formation in less than one minute from application of the composition to the surface. The catalytic composition allows for the water-based polymeric composition to form a film without added heat and without the use of wax. The terms wax free composition, free of wax, without wax is intended to mean a polymeric composition, and resultant film with less than 0.1% wax, typically with 0% wax.
The film-forming polymeric composition of the invention may optionally comprise a tackifier resin, such as an aqueous dispersion of glycerol ester of hydrogenated rosin.
The film-forming polymeric composition of the invention may optionally comprise a filler selected from the group consisting of delaminated clays, kaolin, mica, talc or a mixture, silicate, calcium silicate, calcium carbonate, aluminium hydrate, and mixtures thereof.
The film-forming polymeric composition of the invention may optionally comprise an internal sizing agent, for example an alkyl ketone dimer (AKD) and or an alkyl succinic anhydride (ASA).
The film-forming polymeric composition of the invention may optionally comprise a dispersing agent, a thickener agent, a defoaming agent, a slip agent, an antiskid agent, rheology modifiers, pigments, susceptor materials, crosslinking agents, catalysts, flame retardants, biocides, and wetting agent.
Pigment may be added to the film-forming composition to give the surface of the coated substrate or sheet material a desired appearance. For example, it may be desired that a food-contacting surface of the coated sheet material be a white color. In the event brown kraft paper is used as the substrate sheet material, titanium dioxide may be added to the barrier coating composition to make it white and to make the food-contacting surface of the sheet material white when the barrier coating composition is applied. Pigments such as TI-PURE® 900, a titanium dioxide pigment made by DuPont, are suitable pigments for the barrier coating. Other pigments or dispersions may be suitable so long as they do not significantly degrade the performance of the barrier coating composition.
A dispersing agent may be added to the film-forming composition to help disperse and suspend any component, including fillers and pigment particles, in the composition before application, and to stabilize the suspension. Any of a variety of dispersing agents may be used. For example, dispersing agents such as tetra sodium pyrophosphate ("TSPP") and sodium hexa meta phosphate are suitable for this purpose. It may be desirable to add a minor amount of fine metal powder or flakes, such as aluminum powder or flakes, to the barrier coating composition or release coating composition as a susceptor material.
The fast drying film formation barrier coatings composition suitably comprises, in weight % to a total of 100%, the following:
- Stearate calcium, aluminium or zinc dispersion: 5 to 55%, preferably 17 to 27% - C11-Ci8 fatty acid complex of a metal ion (Quilon L, C or S): 0.2 to 7.5%, preferably 1 to 3%
- Dispersion of polymer or a mixture: 25 to 80%, preferably 80 to 50%
- Filler as powder or dispersion of slurry: 0 to 30%
- Additives: 0 to 5%, preferably 0 to 3%
The film-forming composition of the invention is applied, without the need for added thermal energy, in the form of a solution, dispersion, emulsion, suspension, or in a solvent-free form to the surface of a material for film-formation. The material may be cellulose-based, metallic, textile, cement, sand, stone or glass. Cellulose-based materials include paper, card, wood of all sorts, including paperboard, kraft paper. Some of the numerous uses include use in frozen-foods, food packaging, paper for baking, corrugated paperboard, cardboard boxes, wrapping materials for consumable and non-consumable goods, such as hamburgers and sandwiches, such as in fast-food outlets. Metallic surfaces, such as pans, pots and baking trays, each comprising a film prepared from a film-forming composition of the invention, are also anticipated. Furniture and wood- based building materials, each comprising a film prepared from a film-forming composition of the invention, are also anticipated. Cement, outdoor tiling, pavement and the like, each comprising a film prepared from a film- forming composition of the invention, are also anticipated.
While the use of component ii) hereinbefore, namely, the polyvinyl alcohol and/or C9-C18 fatty acid complex of a metal ion is preferred, it is found that acceptable film forming compositions are provided by components i) and iii) described hereinbefore, in accordance with the invention, especially when component i) is in a relatively high concentration. Typically these compositions will improve 20 to 40% by weight of component i) and 80 to 60% of component iii) to a total of 100%.
EXAMPLES
In order to illustrate the foregoing novel compositions, the following examples are provided to further teach preferred embodiments of the invention. The novel water based barrier coating compositions are express in weight % to a total of 100%.
Example 1
Devflo 50C: 18.0% Quilon C: 2.0%
Styronal 4606X: 80.0% (trade mark for an aqueous styrene-butadiene dispersion)
Example 2
Devflo 50C: 17.5%
Quilon C: 2.5% Styronal 4606X: 40.0% Acronal S728: 40.0% (trade mark for an aqueous dispersion of styrene n-butyl acrylate)
Example 3
Devflo 50C: 17.5% Quilon C: 2.5% Styronal 4606X: 50.0% Alsibronz 39: 10.0% Polyplate P: 10.0% Polygloss 90: 19.6% Tamol 850: 0.2% (trade mark for a naphthalene sulfonic acid condensation product) Defoamer colloid 963: 0.2%
Example 4
Devflo50LPH: 18.0% Quilon C: 2.0%
Styronal 4606X : 80.0%
Example 5
Devflo 50LPH : 17.5%
Quilon C : 2.5%
Styronal 4606X : 40.0%
Acronal S728: 40.0%
Example 6
Devflo50LPH: 17.5% Quilon C: 2.5%
Styronal 4606X: 50.0%
Alsibronz 39: 10.0%
Polyplate P: 10.0 % Polygloss 90: 19.6%
Tamol 850: 0.2%
Defoamer colloid 963: 0.2%
Example 7
Devflo 40 RZl : 18.0%
Quilon C: 2.0%
Styronal 4606X: 80.0%
Example 8
Quilon C ... 7.2 to 0.2 %
PVOH as an aqueous solution at 10 % ... 16.8 to 1.8 %
Stearate dispersion as Devflo 50C ... 36.0 to 18.0 % Dispersion of polymers or copolymers as Styronal 4606X ... 40.0 to 80.0 %
Example 9
PVOH as an aqueous solution at 10 wt.% ... 6.0 to 10.0 % Stearate Devflo 50C ... 54.0 to 10.0 %
Dispersion of polymers or copolymers as Styronal 4606X ... 40.0 to 80.0 %
All percentages herein are by weight unless otherwise indicated.

Claims

1. The use of i) a salt of one or more of myristic, palmitic and stearic acid; and ii) polyvinyl alcohol for the formation of wax-free coat or film.
2. The use of i) a salt of one or more of myristic, palmitic and stearic acid; ii) polyvinyl alcohol and iii) a Cg-C is fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3, for the formation of wax-free coat or film.
3. A composition comprising a salt of one or more of myristic, palmitic and stearic acid; and ii) polyvinyl alcohol.
4. A composition comprising a salt of one or more of myristic, palmitic and stearic acid; ii) polyvinyl alcohol; and iii) a C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
5. The composition according to claim 3 or 4, in the form of a dispersion, emulsion, solution, or suspension.
6. The composition according to any one of claims 3 to 5, wherein the salt of one or more of myristic, palmitic and stearic acid is selected from the group consisting of calcium stearate and zinc stearate.
7. The composition according to any one of claims 4 to 6, wherein the C9-C18 fatty acid complex of a metal ion is a chromium-Cg-Cis fatty acid complex.
8. A composition comprising a) a salt of one or more of myristic, palmitic and stearic acid; b) polyvinyl alcohol; and c) a polymeric composition comprising a polymer, copolymer, mixtures of polymers or copolymers.
9. A composition according to claim 8, further comprising d) a C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
10. The composition according to claim 8 or 9 in the form of a dispersion, emulsion, solution, or suspension.
1 1. The composition according to any one of claims 8 to 10, wherein the polymeric composition comprises a polymer, copolymer or a mixture of polymers or copolymers selected from the group consisting of styrene butadiene copolymers, modified styrene butadiene copolymers, styrene / acrylate copolymers, carboxylated polystyrene, acrylic / polyacrylic polymers, polyvinyl acetate; polyvinyl alcohol, polyvinylacetate-ethylene, polyvinyl acrylic; soy protein polymer; corn zein (protein), starch, polyolefin dispersion as modified propylene-based dispersion; and polyvinylidene chloride.
12. The composition of claim 8, comprising 20 to 40% by weight of a) and 80 to 60% by weight of b) and c).
13. A process for providing water, vapour, oil and grease resistance to a material comprising I. combining a) a salt of one or more of myristic, palmitic and stearic acid; b) polyvinyl alcohol; and c) a polymeric composition comprising a polymer, copolymer, mixtures of polymers or copolymers and II. allowing a film to form on the material at a temperature less than 5O0C.
14. The process of claim 13, wherein step I) further comprises combining a), b) and c) with d) a Cg-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
15. The process of claim 13, wherein in step I), a) comprises 20 to 40% by weight and b) and c) comprises 80 to 60% by weight.
16. The process of claim 13, wherein said salt in a) is calcium stearate.
17. The process of claim 14, wherein a) and d) are in a ratio of 5:1 to 20:1.
18. A process for providing water, vapour, oil and grease resistance to a material comprising a. combining i) a salt of one or more of myristic, palmitic and stearic acid; ii) polyvinyl alcohol a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3; and iii) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers and b. allowing a film to form without added thermal or microwave energy.
19. The process of claim 18, wherein a C9-Ci8 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3 is combined with i), ii), and iii).
20. A material comprising a substrate having a surface with a film coating formed by coating the surface with a film forming composition comprising a) a salt of one or more of myristic, palmitic and stearic acid; b) polyvinyl alcohol and c) a polymeric composition comprising a polymer, copolymer, or a mixture of polymers or copolymers; and allowing the film coating to form at a temperature less than 5O0C.
21. The material according to claim 20, wherein the film forming composition further comprises d) a C9-C18 fatty acid complex of a metal ion, said metal ion having an oxidation state of at least 3.
22. The material according to claim 20 wherein said film forming composition comprises 20 to 40% by weight of a) and 80 to 60% by weight of b) and c).
23. The material according to any one of claims 20 to 22, wherein the substrate is selected from a cellulose based material, a metallic based material, a glass based material, a textile based material, concrete material, wood material and building product material.
PCT/CA2010/000847 2009-06-04 2010-06-02 Fast film forming water based barrier coating WO2010139070A1 (en)

Priority Applications (6)

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JP2012513424A JP2012528900A (en) 2009-06-04 2010-06-02 High speed film forming aqueous barrier coating
BRPI1011998A BRPI1011998A2 (en) 2009-06-04 2010-06-02 "rapidly forming water barrier coating"
EP10782873.3A EP2438116A4 (en) 2009-06-04 2010-06-02 Fast film forming water based barrier coating
US13/375,792 US20120135652A1 (en) 2009-06-04 2010-06-02 Fast film forming water based barrier coating
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WO2017115009A1 (en) 2015-12-31 2017-07-06 Kemira Oyj Water-based barrier coatings
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WO2021224881A1 (en) * 2020-05-08 2021-11-11 Greentech Global Pte. Ltd. Methods for biobased derivatization of cellulosic and synthetic materials and articles obtained therefrom

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US20120135652A1 (en) 2012-05-31
JP2012528900A (en) 2012-11-15
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EP2438116A1 (en) 2012-04-11
BRPI1011998A2 (en) 2016-05-10

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