WO2020132519A1 - Article comprenant une couche de finition à base d'eau - Google Patents

Article comprenant une couche de finition à base d'eau Download PDF

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Publication number
WO2020132519A1
WO2020132519A1 PCT/US2019/067974 US2019067974W WO2020132519A1 WO 2020132519 A1 WO2020132519 A1 WO 2020132519A1 US 2019067974 W US2019067974 W US 2019067974W WO 2020132519 A1 WO2020132519 A1 WO 2020132519A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
copolymers
polymer
vinyl acetate
substrate
Prior art date
Application number
PCT/US2019/067974
Other languages
English (en)
Inventor
John D. Clay
Stephen Armstrong
George S. Leotsakos
Michael Jablon
Wen B. Chiao
Rakesh Vig
Gerald Smith
Original Assignee
Honeywell International Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/230,781 external-priority patent/US20190127594A1/en
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Priority to JP2021536021A priority Critical patent/JP7379492B2/ja
Priority to EP19898267.0A priority patent/EP3898794A4/fr
Priority to CN201980090067.XA priority patent/CN113412303A/zh
Priority to KR1020217022792A priority patent/KR20210094133A/ko
Publication of WO2020132519A1 publication Critical patent/WO2020132519A1/fr

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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
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0869—Acids or derivatives thereof
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0853—Vinylacetate
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/30—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by oxidation
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D7/20—Diluents or solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2501/00—Varnish or unspecified clear coat
    • B05D2501/10—Wax
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the disclosure relates to an article that includes a water-based top-coat. More specifically, the top-coat is disposed on and in direct contact with a substrate.
  • Adhesives, inks and coatings are widely used in industry.
  • water- based formulations of such materials are advantageous in terms of cost and toxicological properties, and potentially have greater acceptance as renewable and so-called “green” alternatives to solvent-based and hot melt adhesive formulations.
  • Water-based adhesives, pressure sensitive adhesives and sealants may be formulated with a wide range of synthetic and natural polymer chemistries. For simplicity these product groups are simply described as“adhesives” herein.
  • paper, board and related products e.g. converting and packaging, disposable non- wovens, hygiene products, pressure sensitives, corrugated board and remoistenable adhesives; leather and textiles, e.g. seaming and stitching, lamination, fabric repair and bonding of underlays, rugs and carpets;
  • DIY consumer and“Do It Yourself’
  • woodworking and joinery e.g. cabinet making, furniture manufacture, door and window frame manufacture, structural joinery, upholstery, plywood, particle board and laminates;
  • Heat seal adhesives belong to a class of materials that produce films or coatings upon drying.
  • Heat seal adhesives are thermoplastic materials that can be coated onto a substrate, dried, and then reactivated by heat and pressure. Upon drying, they form a coating that can be heat-activated and bonded to other substrates, such as the foil seal on a commercial yogurt container. They are non-tacky materials at ambient temperature and become molten liquids upon heat activation during the product assembly process. They differ from conventional hot melt adhesives, which that are applied in a molten state and cooled between substrates.
  • Heat seal adhesives have been commonly used in the packaging industry, including for film laminating, pouch construction and blister-pack sealing.
  • the present disclosure provides an adhesion composition.
  • adhesion composition refers to a composition that provides adhesive and/or cohesive properties, and preferably both, and can be used to bond or adhere, including releasabley bond or adhere, to one or more surfaces or materials.
  • the present adhesion compositions can be utilized as an additive to or a component of a composition which can benefit from and/or require the beneficial properties, including adhesion properties, imparted by the present compositions.
  • the present adhesion compositions are used in certain preferred embodiments as an additive and/or a component of water-based adhesives, water-based inks, water-based paints, water-based coatings and the like.
  • the present adhesion composition comprises: (a) a first polymer selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinylacetate, vinyl acetate copolymers, ethylene-(meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene-(meth)acrylate copolymers, polyesters, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, copolymers of any two or more thereof and combinations of any two or more thereof; (b) a second polymer different than said first polymer, and preferably having a molecular weight different than
  • the polymer components (a) and (b) are present in the composition in the form of solid particles having a D50 particle size of from about 10 nanometers (nm) to about 2000 nm, preferably about 10 to about 1000 nm; more preferably about 30 to about 600 nm; still more preferably about 50 to about 500 nm.
  • the first polymer is selected from the group consisting of acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene vinyl acetate, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch and combinations of two or more thereof.
  • the adhesion composition further comprises one or more additives (e) selected from the group consisting of natural and synthetic tackifiers, synthetic polymers such as polybutadienes, polyisobutylenes, polyisoprenes and styrene block copolymers, silicon-based MQ resins, anti-oxidants, stabilizers, fillers, wetting agents and defoaming agents.
  • the tackifier is a resin selected from the group consisting of rosin ester resin, rosin acid resin, synthetic hydrocarbon resin, synthetic terpenic resin and combinations of two or more thereof.
  • the solids content, and preferably the content of components (a) and (b), in the adhesion composition is greater than about 50%; in certain other embodiments, the solids content is about 30% to about 60%.
  • the reference to % used in respect to the adhesion composition refers to the percentage by weight of components a) through d) plus additive(s) e), if present, of the adhesion composition.
  • the first polymer is present in the adhesion composition in an amount of between about 50 % and about 98.5 % of the adhesion composition; a tackifier, if present, comprises from greater than about 0 % and about 40 %; and the second polymer comprised from about 2.5 % to about 25 %.
  • the second polymer comprises, preferably consists essentially of, and more preferably consists of ethylene-acrylic acid copolymer.
  • the number average molecular weight of the first polymer of the adhesion composition is greater than about 500,000 Daltons. In some embodiments, the number average molecular weight of the first polymer is less than about 100,000 Daltons, preferably greater than about 25,000 Daltons and less than about 100,000 Daltons. In some embodiments, the number average molecular weight of the first polymer of the adhesion composition is at least about 50,000 Daltons. In other embodiments, the number average molecular weight of the first polymer is between about 1,000 and about 20,000 Daltons. For certain applications, the number average molecular weight of the adhesion composition is at least about 100,000 Daltons, or at least about 200,000 Daltons; for these applications a preferred range is about 250,000 to about 1,500,000 Daltons.
  • the adhesion composition comprises at least a portion of a pressure sensitive adhesive (PSA)
  • the number average molecular weight of the first polymer of the adhesion composition is at least about 100,000 Daltons, preferably at least about 200,000 Daltons; and is preferably in the range of about 250,000 to about 1,500,000 Daltons.
  • the number average molecular weight of the first polymer is greater than about 500,000 Daltons.
  • the adhesion composition of the present disclosure may be used to enhance the adhesion characteristics of numerous materials and composition, and all such uses are within the broad scope of the present disclosure.
  • each of the following types of materials and compositions can benefit by containing, or in some cases consisting essentially of or consisting of, the adhesion compositions of the present disclosure, especially and preferably when such materials and compositions are water-based materials and compositions: heat seal adhesives; water-based inks; primer compositions; intercoat compositions; basecoat compositions; top coat compositions; clear coat compositions; sealer compositions; aqueous tie layers, overprint varnishes, rheological agents, water-based sealing materials for metal cans, and water-based sprayed can coatings.
  • the foregoing and other materials are believed to achieve particular benefit to adhesion properties for those methods and applications in which the material is applied to or onto a low-energy substrate(s).
  • the adhesion composition of the present disclosure comprises a first polymer component a) having a number average molecular weight greater than about 50,000 Daltons and a second polymer b) which preferably has a number average molecular weight of less than about 20,000 Daltons.
  • the adhesion composition of the present disclosure comprises a first polymer component having a number average molecular weight greater than about 50,000 Daltons.
  • Certain embodiments are directed to methods of improving the cohesive and/or adhesive strength of certain materials and compositions, including particularly and preferably water-based materials and compositions, such as adhesives and the other materials and composition mentioned hereinabove, comprising adding an adhesion composition of the present disclosure to such a water-based material or compositions in amounts and under conditions effective to increase, and preferably substantially increase, at least one of cohesive and adhesive strength, and preferably both, relative to the same composition without the adhesive composition of the present disclosure.
  • the present disclosure is directed to a method of improving the adhesion of a paint or ink, comprising adding adhesion composition of the present disclosure to a water-based paint or ink in amounts and under conditions such that adhesion to a low energy substrate surface is increased, and preferably adhesion to a high- energy substrate is increased as well.
  • the paint in certain embodiments is preferably selected from the group consisting of a primer, an intercoat, a basecoat, a top coat, a clear coat, a sealer, an aqueous tie layer, and an overprint varnish.
  • the ink is preferably selected in certain embodiments from the group consisting of a water-based packaging ink, a water-based printing ink and a water-based flexographic ink.
  • an article in yet another embodiment includes a substrate and a top-coat composition wherein the top-coat composition has a first side disposed on and in direct contact with the substrate and a second side that is outermost and exposed to the environment.
  • the top-coat composition includes:
  • a first polymer selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinylacetate, vinyl acetate copolymers, ethylene-(meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene- (meth)acrylate copolymers, polyesters, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, copolymers of two or more thereof and combinations of two or more thereof; and combinations of any two or more thereof;
  • a second polymer different than the first polymer selected from the group consisting of ethylene-acrylic acid copolymers, oxidized polyethylenes, ethyl ene-vinyl acetate copolymers, oxidized ethylene-vinyl acetate copolymers, maleated polyolefins, homopolymers of polyethylene, homopolymers of polypropylene, and combinations of any two or more thereof; and
  • a cured article includes a substrate and a cured top-coat composition having a first side disposed on and in direct contact with said substrate and a second side that is outermost and exposed to the environment.
  • the cured top-coat includes the cured product of the first polymer.
  • the first polymer is cured in the presence of the second polymer.
  • this disclosure provides a method of forming an article comprising a substrate and a top-coat composition, wherein the top-coat composition has a first side disposed on and in direct contact with the substrate and a second side that is outermost and exposed to the environment.
  • the method includes the steps of providing the substrate, providing an aqueous coating comprising water and a first polymer selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinylacetate, vinyl acetate copolymers, ethylene-(meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene-(meth)acrylate copolymers, polyesters, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, copolymers of two or more thereof and combinations of two or more thereof; and combinations of any two or more thereof, providing an emulsion of water, a surfactant, and a
  • Figure 1 shows a chart of the adhesion properties on different substrates of pressure-sensitive adhesives according to the procedures and materials described in Example 1
  • Figure 2 shows the shear adhesion properties of the same pressure-sensitive adhesives the properties of which are shown in Figure 1, except that the scale of the histogram has been enlarged.
  • Figure 3 shows a chart of the adhesion properties, including the effect of ageing, on different substrates of pressure-sensitive adhesives according to the procedures and materials described in Example 1.
  • Figure 4 shows a chart of the adhesion properties on different substrates of pressure-sensitive adhesives according to the procedures and materials described in Example 1
  • Figure 5 shows a chart of the adhesion properties, including the effect of ageing, on different substrates of pressure-sensitive adhesives according to the procedures and materials described in Example 1.
  • Figure 6 shows a chart of the adhesion properties on different substrates of pressure-sensitive adhesives according to the procedures and materials described in Example 1
  • Figure 7 shows an example of adhesion failure according to the procedure described in Example 14.
  • Figure 8A is a photograph of the paint adhesion results of control samples in the Examples relative to a semi-Gloss white top-coat disposed on corona and non-corona treated substrates.
  • Figure 8B is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes PI disposed on the same substrate.
  • Figure 8C is a photograph of the paint adhesion results of a semi-gloss white top- coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P2 disposed on the same substrate
  • Figure 8D is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P3 disposed on the same substrate.
  • Figure 8E is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P4 disposed on the same substrate.
  • Figure 8F is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a non-corona treated substrate vs. a semi-gloss white top-coat that includes P5 disposed on the same substrate.
  • Figure 8G is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P6 disposed on the same substrate.
  • Figure 8H is a photograph of the paint adhesion results of a corona treated substrate vs. a semi-gloss white top-coat that includes P6 disposed on the same substrate.
  • Figure 81 is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a non-corona treated substrate vs. a semi-gloss white top-coat that includes P7 disposed on the same substrate.
  • Figure 8J is a photograph of the paint adhesion results of a semi-gloss white top- coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P7 disposed on the same substrate.
  • Figure 8K is a photograph of the paint adhesion results of a semi-gloss white top coat disposed on a corona treated substrate vs. a semi-gloss white top-coat that includes P8 disposed on the same substrate.
  • Figure 9A is a photograph of the paint adhesion results of control samples in the
  • Figure 9B is a photograph of the paint adhesion results of an exterior flat white top-coat disposed on a corona treated substrate vs. an exterior flat white top-coat that includes PI disposed on the same substrate.
  • Figure 9C is a photograph of the paint adhesion results of an exterior flat white top-coat disposed on a corona treated substrate vs. an exterior flat white top-coat that includes P3 disposed on the same substrate.
  • Figure 9D is a photograph of the paint adhesion results of an exterior flat white top-coat disposed on a corona treated substrate vs. an exterior flat white top-coat that includes P4 disposed on the same substrate.
  • Figure 9E is a photograph of the paint adhesion results of an exterior flat white top-coat disposed on a corona treated substrate vs. an exterior flat white top-coat that includes P8 disposed on the same substrate.
  • adhesion compositions of the disclosure which preferably contain high solids content and low surfactant concentration, are capable of providing both improved cohesive and adhesive strength when used in a variety of water-based materials and compositions, including adhesives, coatings and inks.
  • inventive adhesion compositions can be added as a component or adhesion promoting agent to another formulation, composition or material in order to provide desirable properties.
  • the present disclosure thus includes a variety of materials and composition, preferably water-based materials and composition, including particularly water-based adhesives, coatings, inks and the like which preferably comprise the adhesion composition of the present disclosure (i.e., components (a) through (e) as described above) in amounts of from about 1% to about 25% by weight, preferably from about 2% to about 20% by weight, more preferably from about 5% to about 15% by weight, based on the weight of all the components in the water-based material or composition, including adhesive, coating or ink formulation.
  • the adhesion composition of the present disclosure i.e., components (a) through (e) as described above
  • the adhesion compositions are in the form of an emulsion, preferably where components (a) and (b) are emulsified and/or dispersed in the aqueous components.
  • the adhesion emulsion is the ability to achieve a high level of solids in the emulsion, preferably in an amount that is higher than, and more preferably substantially higher than the solids that has been previously commonly used, which provides one or more of, and preferably all of, the following advantages: 1) reduced cost in transportation (since compositions with less water are generally less expensive to ship); 2) faster drying, which occurs since there is less water required to evaporate; 3) higher film thicknesses; 4) higher substrate protection; 5) better barrier properties; and 6) less total number of coats required to achieve the desired coverage.
  • the preferred adhesion compositions of the present disclosure include solids with a particle size profile that has found to be advantageous.
  • the particle size range that is preferred according to the present disclosure, together with and in view of the other aspects of the present disclosure, preferably has the advantage of providing improved mar, abrasion and burnish resistance, while preferably at the same time not causing a deterioration of coating gloss.
  • the inventive adhesion compositions of the present disclosure provide solids, and preferably first component (a) and second component (b) in the form of solid particulates, having a D50 particle size of from about 10 nm to about 2000 nm, preferably about 25 to about 1000 nm; more preferably about 50 to about 600 nm; still more preferably about 100 to about 500 nm.
  • the D50 particle size is greater than about 100 nm and less than about 1000 nm.
  • the D50 particle size is greater than about 200 nm and less than about 700 nm.
  • the D50 particle size is greater than about 300 nm and less than about 600 nm.
  • the adhesion composition including the emulsion composition, the solids thereof, and preferably first component (a) and second component (b) in the form of solid particulates, have a particle size distribution: with a D10 of about 10 nm or greater and a D90 of about 2000 nm or less; more preferably with a D10 of about 25 or greater and a D90 of about 1000 nm or less; even more preferably with a D10 of about 50 or greater and a D90 of about 600 nm or less; and still more preferably with a D10 of about 100 or greater and a D90 of about 500 nm or less.
  • the particle size distribution has a D10 of about 100 nm or greater and D90 of about 1000 nm or less. In other embodiments, the particle size distribution has a D10 of about 200 nm or greater and a D90 of about 700 nm or less. In still other embodiments, the particle size has a distribution with a D10 of about 300 nm or greater and a D90 of about 600 nm or less.
  • Applicants have surprisingly found that certain of the preferred embodiments of the present adhesion compositions are able to achieve effective adhesion and/or cohesion enhancement with an advantageously low concentration of surfactant. More specifically, the unexpected ability to use low surfactant concentrations according to the present disclosure, and particularly for the emulsion forms of the adhesion compositions, has the advantage of assisting in the formation of dried coatings and films that have excellent water resistance (lower tendency to absorb water from the environment after the coating has been dried) and/or enhanced film-forming ability.
  • the adhesion compositions preferably contain surfactant amounts of from greater than about 0% to about 10 %, more preferably from about 0.001% to about 5 %, even more preferably from about 0.01% to about 1 %, and still more preferably from about 0.05% to about 0.5 %.
  • the amount of surfactant contained in the adhesion composition is less than about 5 %, more preferably less than about 3 %, and even more preferably less than about 1 %.
  • the present adhesion compositions comprise surfactant in an amount less than about 0.5 %, preferably less than about 0.1 %, more preferably less than about 0.05 %, and still more preferably less than about 0.01 %.
  • Preferred water-based synthetic polymers contemplated for use according to the present disclosure include: acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene vinyl acetate, natural rubber, neoprene, phenolic resins, polyurethanes, polyvinyl acetate, polyvinyl alcohol and styrene-butadiene rubber.
  • Preferred water-based natural polymers contemplated for use according to the present disclosure include carbohydrate and protein bio-macromolecules such as casein, cellulosics, dextrin and starch.
  • the present adhesion formulations preferably comprise (a) a first polymer as disclosed above; (b) a second polymer as disclosed above; (c) other functional components such as surfactants; (d) water; and (e) optionally other additives.
  • the polymers, and potentially other functional components are preferably present as solid particles dispersed in water, preferably with a particle size distribution as described herein. Although it is possible that some percentage of the solid components (a) and (b) may be present as solutes in the water/aqueous solvent, this is generally not preferred.
  • the first polymer of the adhesion composition is preferably selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene vinyl acetate, natural rubber, neoprene, phenolics, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene-butadiene rubber, casein, and polysaccharides such as dextrin and starch.
  • the second polymer is preferably selected from the group consisting of homopolymer polyethylene (PE) waxes, homopolymer polypropylene (PP) waxes, ethylene-propylene copolymer waxes, oxidized PE homopolymer waxes; EAA copolymer waxes, EVA copolymer waxes, oxidized EVA copolymer waxes, PE waxes grafted with maleic anhydride and PP waxes grafted with maleic anhydride.
  • PE polyethylene
  • PP homopolymer polypropylene
  • ethylene-propylene copolymer waxes ethylene-propylene copolymer waxes
  • oxidized PE homopolymer waxes EAA copolymer waxes, EVA copolymer waxes, oxidized EVA copolymer waxes, PE waxes grafted with maleic anhydride and PP waxes grafted with maleic anhydride.
  • the other functional components can optionally be included in the adhesion compositions of the present disclosure.
  • the other functional components are selected from the group consisting of natural tackifying resins, synthetic tackifying resins, polybutadiene, functionalized polybutadienes, polyisobutylene, functionalized polyisobutylene, polyisoprene, functionalized polyisoprene, styrene block copolymers with butadiene, styrene block copolymers with isoprene, styrene block copolymers with ethylene-butadiene rubber blocks, uncapped silicone MQ resins and capped silicone MQ resins, thickeners, wetting agents, antifoam agents, antioxidants, pigments, fillers and combinations of any two or more of these.
  • Viscosity The adhesive viscosity is low enough to allow easy handling and processing, but not too low, so as to avoid excessive penetration into porous substrates, nor too high, such that the wetting of substrates is retarded.
  • Dry Content The solids content of the adhesive can be raised as high as practically needed/possible to allow drying within an acceptable period of time for any given bond forming process.
  • One aspect of the present disclosure is directed to novel water-based dispersions and/or emulsions of one or more polymers and resins selected from homopolymer polyethylene waxes, homopolymer polypropylene waxes, ethylene-propylene copolymer waxes, oxidized polyethylene homopolymer waxes, ethylene acrylic acid copolymer waxes, ethylene vinyl acetate waxes, oxidized vinyl acetate copolymer waxes, polyethylene waxes grafted with maleic anhydride, polypropylene waxes grafted with maleic anhydride, natural and synthetic tackifying resins, polybutadiene and functionalized polybutadiene, polyisoprene and functionalized polyisoprenes, polyisobutylene and functionalized polyisobutylene, styrene block copolymers and silicon-based MQ resins.
  • polymers and resins selected from homopolymer polyethylene waxes, homopolymer polypropy
  • adhesion composition of the present disclosure into a water- based material or composition to act as an adhesion enhancing agent permits the formulation of higher performing products, which may be based on either synthetic or natural polymer chemistries.
  • these environmentally favorable products can be used in more demanding applications that have traditionally been served with less sustainable technologies, and in particular allows the expanded use of sustainable natural raw materials in adhesive formulations.
  • Such adhesives are characterized by increased elastic and loss moduli as well as a capacity to maintain their physical characteristics over a broader temperature range, compared to the unmodified adhesive polymer.
  • the number average molecular weight of the first polymer in many preferred adhesion composition embodiments of the present disclosure is not less than about 100,000 Daltons.
  • the first polymer of the adhesion composition has a number average molecular weight that is less than about 250,000 Daltons, and more preferably less than about 100,000 Daltons.
  • the number average molecular weight of the first polymers present in the adhesion composition of the present disclosure is about 50,000 to about 100,000 Daltons.
  • heat seal adhesives can be applied by a variety of coating techniques, including coating via gravure, slot die or extrusion processes.
  • Low melting polymers such as EVA, acrylic polymers, vinyl acetate copolymers, polyurethanes, polyesters and the like, are preferably used for heat seal adhesives, and the present adhesion composition is preferably added to those materials, preferably by mixing, to form a heat seal adhesive with enhanced adhesion and/or cohesion properties.
  • a high performance heat seal adhesive for commercial usage should provide the properties of remaining non-tacky up to 130°F, having low heat activation temperature of 180-300°F, having hot green strength of at least about 1 psi to difficult-to-bond substrates, such as PP, PE, PET and aluminum foil.
  • high performance heat seal adhesives are prepared by incorporating emulsions of low molecular weight ethylene- acrylic copolymers, oxidized polyethylenes, ethylene-vinyl acetate copolymers, oxidized ethylene-vinyl acetate copolymers, maleated polyolefins, homopolymers of PE, PP waxes, and combinations of these in formulations which offer the benefits of anti -blocking, low activation temperature bonding and improved adhesion to difficult-to-bond substrates and high hot green strength.
  • the adhesion composition for use as, with or in addition to a heat seal adhesive composition comprises:
  • a first polymer selected from the group consisting acrylic polymers, ethylene-vinyl acetate copolymers, modified EVA, vinyl acetate copolymers, polyurethanes, ethylene- (meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene-(meth)acrylate copolymers, polyesters and combinations of two or more thereof; and
  • a second polymer selected from the group consisting ethylene-acrylic acid copolymers, oxidized polyethylenes, ethyl ene-vinyl acetate copolymers, oxidized ethylene- vinyl acetate copolymers, maleated polyolefins , homopolymers of PE and PP, and combinations of two or more thereof;
  • additives such as tackifiers, anti-blocking agents, anti -oxidants, stabilizers, fillers, wetting agents;
  • an adhesion composition of the present disclosure preferably in the form of an emulsion of the present disclosure, can in many embodiments provide an improvement in adhesive qualities to aqueous primers, based on its aqueous compatibility and adhesion boosting characteristics.
  • aqueous primers when such primers were applied over low-energy substrates difficulty was encountered in that the primer did not adequately wet that substrate and adhere to it.
  • the addition of a preferred adhesion composition, an even more preferably an adhesion emulsion of the disclosure is capable of rectifying problems such as those and others.
  • adhesion of the successive coats can be challenging.
  • inventive adhesion composition and preferably an adhesion emulsion of the present disclosure, to the aqueous top coat boosts adhesion to the lower surface energy primer resulting in a better bond.
  • Aqueous tie layer :
  • the adhesion composition and preferably an adhesion emulsion of the present disclosure, with its adhesive qualities, can by itself, serve as a water-based tie layer between two similar or dissimilar substrates. It can also be added to another adhesive composition to provide an aqueous tie layer composition.
  • OP Vs Print Varnishes
  • Typical high gloss clear coatings need good water, mar, burnish and abrasion resistance.
  • OVPs have required aqueous waxes, typically high density oxidized ones in emulsion form in order to provide these properties to the typically acrylic-based OPV.
  • the adhesion composition, and preferably an adhesion emulsion of the present disclosure has a preferred particle size that is small enough to retain clarity and be gloss neutral, but provide a higher level of mar, burnish and abrasion resistance than a microemulsion. Further, the addition of the present adhesion composition/emulsion does not detract from gloss or clarity as micronized waxes tend to do.
  • compositions of the disclosure where the first polymer or copolymer has a number average molecular weight of less than about 20,000 Daltons, preferably less than about 12,000 Daltons, show efficacy when used as water-based and/or water reducible rheological control agents and/or as an additive in other compositions that are used or applied as water- based and/or water reducible rheological control agents.
  • the first polymer of the present adhesion composition has a number average molecular weight of less than about 1,000 Daltons.
  • adhesion composition of the present disclosure and preferably such a composition that includes polyethylene-based polymer, as rheological control agent or an additive thereto, compared to what is currently in the market place are many fold, including 1) not prone to microbial attack; 2) not pH sensitive; 3) not shear sensitive; 4) provides ease of incorporation (liquid to liquid), with no exfoliation or activating solvents necessary; and 5) is thixotropic providing the best rheological profile for coatings and shows efficacy in water-based and/or water reducible rheological control.
  • the first polymer is EAA or a metal ionomer thereof.
  • Water-based sealing compound of metal can ends or lids to the body of metal cans; O-ring seal; end-sealing compounds.
  • the adhesion composition and preferably an adhesion emulsion of the present disclosure, provides benefits as a water-based sealing compound and as component in or additive to other water-based formulations of sealing material (sometimes referred to as a “sealing compound”) of can ends (lids) to the body of cans.
  • the sealing material is enhanced by use of the present adhesion composition, preferably the adhesion emulsion, and is then lined in the annular groove inside the perimeter of the can lid, and forced-air-dried to a “casket” similar to an O-ring configuration.
  • the can lid is subsequently double-seamed to the flanges of the can body to seal the can.
  • Preferred water-based end seaming formulations are primarily comprised of aqueous latex styrene-butadiene rubber (SBR), fillers, tackifiers, dispersing agents and rheology modifying agents.
  • the adhesion composition comprises as the first polymer a) low number average molecular weight (below 10,000 Daltons) acrylic modified polyethylene copolymers (such as EAA), and the composition is preferably in the form of a water-based high solids (30-60%, e.g. 55% solids) emulsion.
  • the present adhesion compositions are capable of providing compatibility and tackifying benefits.
  • this advantage is due, at least in part, to the dual aspects of the formulations, i.e., polar (e.g., acrylic) and non-polar (e.g., polyethylene features).
  • the inventive water-based sealing formulations also provide improved adhesion of the formulations to the metal lids.
  • this advantage is believed to be due, at least in part, to the presence of carboxyl functionality which bonds to metal.
  • the inventive water-based sealing formulations provide faster drying times of the formulation due to the high solids concentration, requiring less time for water removal (low water content). All of these factors combine to increase performance and line speed in can end sealing manufacturing operations. Water-based sprayed can coatings for two-piece cans.
  • Emulsions of the present disclosure can also provide benefits as water-based spray coating and as a component of or additive to such materials, which are coatings used in the interior of beer, beverage or food 2-piece cans. Its carboxyl group functionality can provide reactive sites to further cross-link amine or hydroxyl functional groups available from cross linkers from the binder components, resulting in in situ polymerization under thermoset conditions.
  • the EAA chemistry of the inventive composition comprises low molecular weight (LMW) EAA polymers.
  • LMW low molecular weight
  • the term“low molecular weight” means a number average molecular weight of less than 10,000 Daltons, unless specifically indicated otherwise herein.
  • the polymerization encounters minimal steric hindrance so that the EAA polymer is readily incorporated into the cross-linked polymer network. Any remaining unreacted free carboxyl groups provide added adhesion to the metal can.
  • the inert polyethylene backbone of the EAA provides polymer flexibility, reducing internal polymer stress, which allows for improved flexibility. These traits also allow for downstream fabrication during flanging of the 2-piece body can. Sprayability is assisted by the rheological profile of the inventive composition, allowing for shear thinning during spraying.
  • the inventive compositions also allows for thixotropic recovery of the applied wet film before drying and setting under heat.
  • the high solids feature of the preferred emulsion (30-60%) aids spraying of the formulation to achieve higher film weights per can, when desired.
  • Water-based flexographic inks formulated to be printed onto low-energy substrates are provided.
  • flexographic inks are applied by small-pore anilox rollers as thin films, advantage can be achieved by combining the present adhesive compositions with such inks, especially since the cohesive properties of such materials is considered important.
  • the inventive adhesion composition preferably the adhesion emulsion, is preferably used in such embodiments a component in water-based flexographic formulations, and specifically provides unique benefits for printing on plastic, film and foil substrates. Water-based flexographic inks are widely used on cellulosic and corrugated substrates and most flexographic inks are easily absorbed by these substrates.
  • Non-absorbing substrates require reformulated water- based flexographic inks that have lower surface tension than the substrates that are printed, that wet low-energy substrates readily, and that adhere to the substrate upon curing (hot air).
  • inventive compositions address these needs and enable the formulation of high solids, low surface energy, water-based inks with desirable rheology for printing low energy substrates.
  • the adhesion compositions contain an acrylate polymer and a tackifier.
  • Acrylate polymers are commonly used to improve cohesion of the pressure-sensitive adhesive and resistance to shear.
  • Tackifiers are commonly used to improve adhesion.
  • the term tackifier usually refers to a low molecular weight resin with a number average molecular weight in the range between about 270 and about 1400 Daltons. Most commercially available tackifiers have a number average molecular weight that is in the range between about 800 and about 1200 Daltons. Molecules with number average molecular weights of greater than about 2000 Daltons are normally referred to as polymers.
  • tackifiers are commonly based on rosin esters, but might also be based on rosin acids, dimerised rosin acids and certain types of synthetic resins such as terpenic resins and C9/C5 hydrocarbon resins. Tackifiers improve peel adhesion to“difficult- to-bond substrates,” such as polyethylene, and they also improve quick stick (tack) properties to low-energy and high-energy surfaces. There are, however, a number of drawbacks to using tackifier resins. Tackifier resins need to be dispersed with a much higher concentration of surfactants than polymer systems. Excess surfactant absorbs moisture, which can negatively impact the convertibility of the pressure-sensitive adhesive.
  • resins are super cooled liquids, which exhibit a tendency to flow. This leads to sticky edges and gumming of knives. Additionally, the low molecular weight of resins allows them to migrate into paper substrates, leading to loss of adhesion. This effect is augmented by heat and humidity.
  • adhesives can be manufactured that contain less rosin- based tackifier than many commercially available adhesives and are therefore less prone to the above-mentioned problems, by using the adhesion composition, and particularly the adhesion emulsion, of the present disclosure. Additionally, the adhesives which incorporate the adhesion composition of the present disclosure have overall better cohesion and shear resistance, and, at the same time, similar or better adhesion to certain difficult substrates, particularly after aging, than adhesives made without the present compositions but containing primarily acrylate polymer and rosin ester.
  • the present disclosure also provides a water-based composition that is adapted for adhesion to low-energy substrates.
  • This composition comprises a first polymer that is selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene vinyl acetate, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, copolymers of two or more thereof and combinations of two or more hereof.
  • the composition of the present disclosure also comprises a tackifier resin selected from the group consisting of rosin ester resin, rosin acid resin, synthetic hydrocarbon resin, synthetic terpenic resin and combinations of two or more thereof.
  • the composition of the present disclosure also comprises a second polymer selected from the group consisting of ethylene-acrylic acid copolymer, oxidized polyethylene, oxidized ethylene-vinyl acetate copolymer, maleated polyolefin and combinations of two or more thereof.
  • Acrylate polymers (polymers composed of acrylic acid or acrylic acid derivates) and copolymers (co-polymers composed of acrylic acid or acrylic acid derivates) are conventionally used in the art of pressure-sensitive adhesives and the types of acrylate polymers and copolymers that can be used in the present disclosure are not particularly limited.
  • alkyl acrylates and alkyl methacrylates which in combination may be designated as “alkyl (meth)acrylate,” are preferably used as the major monomer component in the acrylate polymers and copolymers of the present disclosure.
  • alkyl (meth)acrylates are represented by the following general formula:
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents an alkyl group.
  • alkyl group for R2 include linear or branched alkyl groups having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, an isoamyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl (lauryl) group, a tridec
  • alkyl(meth)acrylates examples include methyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, s-butyl(meth)acrylate, t-butyl(meth)acrylate, pentyl(meth)acrylate, isoamyl(meth)acrylate, neopentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, nonyl(meth)acrylate, isononyl(meth)acrylate, decyl (meth)acryl ate, isodecyl(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate, and the like.
  • alkyl(meth)acrylate as the major constituting monomer component, another minor monomer component that is copolymerizable with the alkyl(meth)acrylate can also be used.
  • the amount of the alkyl(meth)acrylate with respect to the total amount of monomers constituting the acrylate polymer or copolymer is preferably 50% by weight or more. More than one type of alkyl(meth)acrylate can be used in the same acrylate polymer and copolymer.
  • the copolymerizable monomer component can be used for introducing a crosslinking site into the acrylate polymer or for enhancing an aggregating ability of the acrylate polymer.
  • One type or several different types of monomers can be used for copolymerization.
  • monomers containing a certain functional group can be used as the copolymerizable monomer component.
  • the use of the functional group-containing monomer component can enhance the adhesive force of the polymer.
  • Such a functional group-containing monomer component is not particularly limited. It is a monomer component copolymerizable with the alkyl (meth)acrylate, having a functional group which becomes a crosslinking site.
  • Non-limiting examples of such monomers include carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and isocrotonic acid or acid anhydrides thereof such as maleic anhydride and itaconic anhydride; hydroxyl group- containing monomers, e.g., hydroxyalkyl(meth)acrylates such as 2- hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, and 2- hydroxybutyl(meth) acrylate and also vinyl alcohol and allyl alcohol; amide-based monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth) acrylamide, N- methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N- methoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide; amino group
  • Non-limiting examples of the other copolymerizable monomer components include vinyl ester-based monomers such as vinyl acetate and vinyl propionate; styrene -based monomers such as styrene, substituted styrenes (such as ⁇ - methylstyrene and vinyltoluene); non-aromatic ring-containing(meth)acrylate esters such as cycloalkyl(meth)acrylates (such as cyclohexyl(meth)acrylate, cyclopentyl di(meth)acrylate, bomyl(meth)acrylate and isobomyl(meth)acrylate]; aromatic ring-containing (meth)acrylate esters such as aryl(meth)acrylates [e.g.
  • phenyl (meth)acrylate ], aryloxyalkyl(meth)acrylate (e.g. phenoxyethyl(meth)acrylate), and arylalkyl(meth)acrylates (e.g. benzyl(meth)acrylate); olefmic monomers such as ethylene, propylene, isoprene, butadiene, isobutylene, vinyl chloride and vinylidene chloride; isocyanate group -containing monomers, such as 2- (meth)acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl(meth)acrylate and ethoxyethyl(meth) acrylate; vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; and polyfunctional monomers such as 1,6- hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glyco
  • the acrylate polymer or copolymer includes 2-ethylhexyl acrylate and/or butyl acrylate as the major monomer component and methyl methacrylate, vinyl acetate and/or styrene as the minor monomer component.
  • Processes for polymerizing acrylate polymers and acrylate copolymers are generally known in the art. Non-limiting examples of such processes are emulsion (co)polymerization, solution (co)polymerization, suspension (co)polymerization, all- components-charging processes (at once polymerization processes), and monomer-dropping processes (continuously dropping process, portion-wise dropping process).
  • the polymerization initiator to be used is selected from those generally known in the art, according to the type of polymerization process involved.
  • Non-limiting examples of polymerization initiators include azo polymerization initiators such as 2,2'- azobisisobutyronitrile, 2,2'-azobis(2-methylpropion-amidine)disulfate, 2,2'-azobis(2- amidinopropane)dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis(4- methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2- methylbutyronitrile), 1 , 1 '-azobis(cyclohexane- 1 -carbonitrile),
  • Polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator is typical of those commonly used in the art, and can be, for example, selected from the range of about 0.01 to 1 part by weight, preferably 0.02 to 0.5 part by weight, relative to 100 parts by weight of the total monomer components to be polymerized.
  • the polymerization temperature is selected according to the type of monomer, the type of initiator, and the like, as commonly known in the art, and can be, for example, in the range between 20°C and 100°C.
  • the acrylate polymer and acrylate copolymer compositions may be dispersed or emulsified in a medium, for example water. Any suitable emulsifier can be used for that purpose.
  • anionic emulsifiers include alkyl sulfate salt-type anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, and potassium lauryl sulfate; polyoxyethylene alkyl ether sulfate salt-type anionic emulsifiers such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkylphenyl ether sulfate salt-type anionic emulsifiers such as ammonium polyoxyethylene laurylphenyl ether sulfate and sodium polyoxyethylene laurylphenyl ether sulfate; sulfonate salt-type anionic emulsifiers such as sodium dodecyl
  • nonionic emulsifiers include polyoxyethylene alkyl ether- type nonionic emulsifiers such as polyoxyethylene lauryl ether; polyoxyethylene alkylphenyl ether-type nonionic emulsifiers such as polyoxyethylene laurylphenyl ether; nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block polymers; combinations of any two or more of these and the like monomers.
  • the amount of the emulsifier to be used is not particularly limited as far as it is an amount capable of preparing the acrylate polymer or acrylate copolymer in an emulsion form.
  • the amount can be selected from the range of about 0.3 to 10 parts by weight, preferably about 0.5 to 5 parts by weight relative to 100 parts by weight of the acrylate polymer or acrylate copolymer, or monomer components thereof.
  • An acrylate copolymer for use in the present adhesion compositions can be obtained from BASF Corporation, Charlotte, NC, USA, under the trade name ACRONAL® V215.
  • ACRONAL® V215 has the following specification: the solids content is 68 to 70 %; the pH value is 3.5 to 6.0; the viscosity at 23°C (Brookfield RVT, spindle #3, at 50 rpm) is 400 to 2000 cps; the density is about 8.4 lb/gal; the viscosity at 23°C (shear rate 100 sec -1) is 200 to 1000 cps; the mean particle size is about 0.6 pm; the dispersion type is anionic; and the glass transition temperature (DSC) is about 43°C.
  • Another acrylate copolymer useful according to the present compositions is sold by Organik Kimya, Turkey, under the name ORGAL AX1260.
  • Tackifiers are conventionally used in the art of pressure-sensitive adhesives and the type of tackifier that can be used in the present disclosure is not particularly limited.
  • suitable tackifiers include rosin-based tackifying resins, terpene- based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, elastomer-based tackifying resins, phenol-based tackifying resins, ketone-based tackifying resins, and the like.
  • the tackifying resin can be used solely or in combination of two or more thereof.
  • Rosin is a solid form of resin obtained primarily, but not exclusively, from conifers (rosin obtained from this source is sometimes called gum rosin). Other sources of rosin include rosin obtained from the distillation of crude tall oil (called tall oil rosin). Rosin may also be obtained from aged pine stumps (typically called wood rosin). Rosin primarily consists of different rosin acids, especially abietic acid, neoabietic acid, palustric acid, levopimaric acid, dehydroabietic acid, pimaric acid, sandaracopimaric acid and isopimaric acid.
  • abietic acid especially abietic acid, neoabietic acid, palustric acid, levopimaric acid, dehydroabietic acid, pimaric acid, sandaracopimaric acid and isopimaric acid.
  • Rosin-based tackifier resins can include unmodified rosins (raw rosins) such as gum rosins, wood rosins, and tall oil rosins and rosins modified by hydrogenation, disproportionation, polymerization or other processes.
  • raw rosins such as gum rosins, wood rosins, and tall oil rosins and rosins modified by hydrogenation, disproportionation, polymerization or other processes.
  • Non-limiting examples of rosin derivatives include rosin esters obtained by esterifying unmodified rosins and rosin esters obtained by esterifying modified rosins, including, for example, hydrogenated rosins, disproportionated rosins, polymerized rosins, and the like; unsaturated fatty acid-modified rosins obtained by modifying unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, and the like) with unsaturated fatty acids; unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by reducing the carboxyl group in unmodified rosins, modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, and the like), unsaturated fatty acid-modified rosins, or unsaturated fatty acid-
  • rosin phenol resins obtained by adding phenol to rosins (unmodified rosins, modified rosins, and various rosin derivatives, and the like) in the presence of an acid catalyst, followed by thermal polymerization. Rosin-based tackifying resins, and their manufacture, are well known to those skilled in the art. Therefore, these resins and their manufacture are not described herein in greater detail. [0097] Rosin acids and rosin acid-based resins are known to the person of skill in the art and commercially available from many sources, for example DRT (France), Euro-Yser (Portugal), Harima Chemicals, Inc. (Japan), and Eastman Chemical Company (USA).
  • Rosin ester resins are commercially available, for example, from Eastman Chemical Company, Kingsport, TN, USA, under the trade name TACOLYNTM 3509.
  • TACOLYNTM 3509 resin dispersion is an anionic, aqueous, 55% solids, solvent-free dispersion of a stabilized rosin ester with low surface tension.
  • TACOLYNTM 3509 resin dispersion has the following specification: the average particle size is typically 200 nm; the softening point (Hercules drop method) is 68-78°C; the total solids content is 54-56%; the viscosity, Brookfield LVTD, 60 rpm, at 25°C is 100-500 mPa.s; and the density is typically 1.05 g/mL.
  • Rosin dispersion is commercially available, for example, from Arizona Chemical, FL, USA, under the trade name AQUATACTM XR 4343, which has the following specification: the ring and ball softening point is about 80°C; the solids content is about 60%; the pH is typically 8.5; and the viscosity is typically between 500 and 700 cps at Brookfield #3 spindle at 50 rpm at 21°C.
  • Synthetic hydrocarbon resins are the products of the polymerization of the C9 or C9/C5 by-product fractions derived from the cracking or chemical treatment of petroleum. These types of resins are known in the art and commercially available from many sources (e.g., Eastman Chemical Company, Kingsport, TN, USA, under the trade name TACOLYNTM 1070).
  • Synthetic terpenic resins are dispersions of terpene and phenol, or terpene and styrene or styrene-derivatives. These types of resins are known in the art and commercially available from many sources (e.g., DRT, France, and Arizona Chemical, FL, USA).
  • the tackifier may have a form constituted by the tackifying resin alone or may be dissolved or dispersed in a medium-like water.
  • the water-dispersion type tackifier can be prepared by dissolving or melting the tackifying resin and subsequently dispersing it in water.
  • An emulsifier can be employed for the dispersion of the tackifying resin in water. Any suitable type of emulsifier may be used.
  • anionic emulsifiers include alkyl sulfate salt-type anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, and potassium lauryl sulfate; polyoxyethylene alkyl ether sulfate salt-type anionic emulsifiers such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkylphenyl ether sulfate salt-type anionic emulsifiers such as ammonium polyoxyethylene laurylphenyl ether sulfate and sodium polyoxyethylene laurylphenyl ether sulfate; sulfonate salt-type anionic emulsifiers such as sodium dodecylbenzenesulfonate; sulfosuccinate-type anionic emulsifiers such as disodium lauryl sulfosuccinate and disodium lauryl polyoxyethylenes
  • Non-limiting examples of the nonionic emulsifiers include polyoxyethylene alkyl ether- type nonionic emulsifiers such as polyoxyethylene lauryl ether; polyoxyethylene alkylphenyl ether-type nonionic emulsifiers such as polyoxyethylene laurylphenyl ether; nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block polymers; combinations of any two or more of these and the like monomers.
  • Surfactants may also be used for the dispersion of the tackifying resin in water or other medium.
  • the amount of the emulsifier to be used is not particularly limited as far as it is in an amount capable of preparing the tackifying resin in an emulsion form.
  • the amount can be selected from the range of about 0.2 to 10% by weight, preferably from 0.5 to 5% by weight, based on the total amount of the tackifying resin (solid matter).
  • the emulsifier used for the preparation of the water-dispersion type tackifier can be the same as or different from the emulsifier used for the preparation of the water-dispersion type acrylate polymer or acrylate copolymer mentioned above.
  • the ratio by weight between the acrylate polymer and the tackifier resin in the pressure-sensitive adhesive is not particularly limited and can be selected according to the degree of adhesiveness that the pressure-sensitive adhesive is desired to have. In some embodiments of the present disclosure, the ratio by dry weight between the acrylate polymer (or acrylate copolymer) and the tackifier resin is between about 9: 1 and about 8: 1.
  • the ratio is between about 8: 1 and about 7: 1 between about 7: 1 and about 6: 1, between about 6: 1 and about 5: 1, between about 5: 1 and about 4: 1, between about 4: 1 and about 3 : 1, between about 3 : 1 and about 2: 1, between about 2: 1 and about 1 : 1, between about 1 : 1 and about 1 :2, and between about 1 :2 and about 1 :3.
  • the second polymer of the present disclosure is selected from the group consisting of ethylene-acrylic acid copolymer, oxidized polyethylene, oxidized ethylene-vinyl acetate copolymer, maleated polyolefin and combinations of two or more thereof.
  • Ethylene-acrylic acid copolymers are well known to those skilled in the art, as is their manufacture. These copolymers are used for numerous applications. For example, these copolymers are used as additives in adhesives, coatings and inks.
  • Ethylene-acrylic acid copolymers are made by polymerization of ethylene and acrylic acid monomers, usually using a free radical initiator.
  • the acrylic acid content of the copolymer contributes to the copolymer’s polarity and adhesion and lowers its crystallinity. As the content of the acrylic acid monomer subunits in the polymer increases, the crystallinity of ethylene-acrylic acid copolymers decreases.
  • the amount of acrylic acid monomer subunits in the copolymers, or the copolymers’ acid number is determined by method ASTM D-1386. Polymers with high acid number contain high content of acrylic acid monomers.
  • Commercial grades of ethylene-acrylic acid copolymers are available in acid numbers from about 40 to 200 mg KOH/g. The acidic group in the ethylene- acrylic acid copolymers provides reactive sites for the manufacture of water-based emulsions.
  • the number average molecular weight (Mn) of ethylene-acrylic acid copolymers commonly ranges from 1,500 to 3,000 and their weight average molecular weight (Mw) commonly ranges from 2,000 to 6,000.
  • the molecular ethylene-acrylic acid copolymers is determined by Gel Permeation Chromatography (GPC).
  • the density of the polymers commonly ranges from 0.90- 1.00 g. /cc as determined by method ASTM D-1505.
  • the Mettler Drop point of the polymers commonly ranges from 70°C-110°C as determined by method ASTM D-3954.
  • the viscosity at 140°C of ethylene-acrylic acid copolymers commonly ranges from 200-1,000 cps as determined by a Brookfield rotational viscometer.
  • the hardness of the ethylene-acrylic acid copolymers at 25°C commonly ranges from 1-50 dmm as determined by method ASTM D-5.
  • Ethylene-acrylic acid copolymer is commercially available, for example, from Honeywell International Inc., as A-C® 5120.
  • A-C® 5120 has the following specification: the acid number is 112 to 130 mg KOH/g; the penetration hardness value at 25°C is lower than 15 dmm (typically 8 dmm); the viscosity at 140°C (Brookfield) is 600 cps; the drop point (Mettler) is 92°C; and the density is 0.93 g/cc.
  • Oxidized ethylene-vinyl acetate copolymers are well known to those skilled in the art, as is their manufacture.
  • Oxidized ethylene-vinyl acetate copolymers contain polar groups, such as carboxylic acid, hydroxyl, ketone and ester groups, in the polymer molecule.
  • the polymers are made by oxidation of ethylene-vinyl acetate copolymers with oxygen (typically provided in air) at elevated temperatures.
  • Oxidized ethylene-vinyl acetate copolymers are semi-crystalline materials, which contain a variety of polar groups besides carboxylic acid, all of which contribute to the adhesion and water compatibility of the oxidized ethylene-vinyl acetate copolymer.
  • copolymers are used for numerous applications. For example, these copolymers are used as additives in adhesives, coatings and inks.
  • the acid content in oxidized ethyl ene-vinyl acetate copolymers, or the copolymers’ acid number, is determined by method ASTM D-1386.
  • Commercial grades of oxidized ethylene-vinyl acetate copolymers are commonly available in acid numbers from about 8-30 mg KOH/g.
  • the acidic groups in the copolymers provides reactive sites for making water-based emulsions.
  • the number average molecular weight (Mn) of oxidized polyethylenes commonly ranges from 1,500 to 4,000 and their weight average molecular weight (Mw) commonly ranges from 4,000 to 15,000.
  • the molecular weight of oxidized ethylene-vinyl acetate copolymers is determined by Gel Permeation Chromatography(GPC).
  • the density of the copolymers commonly ranges from 0.85-1.00 g/cc as determined by method ASTM D-1505.
  • the Mettler drop point of the copolymers commonly ranges from 75°C-110°C as determined by method ASTM D-3954.
  • the viscosity at 140°C of the copolymers ranges from 250 to 1,500 cps as determined by a Brookfield rotational viscometer.
  • the hardness of the polymers commonly ranges from 3-80 dmm as determined by method ASTM D-5.
  • Oxidized ethylene-vinyl acetate copolymer is commercially available from, for example, Honeywell International Inc. under the trade name A-C® 645P.
  • A-C® 645P has the following specification: the acid number is 12 to 16 mg KOH/g; the hardness at 25°C is 4 to 7 dmm; the viscosity at 140°C (Brookfield) is 375 cps; the drop point (Mettler) is 99°C; and the density is 0.94 g/cc.
  • Oxidized polyethylenes are well known to those skilled in the art, as is their manufacture. Oxidized polyethylenes contain polar groups, such as carboxylic acid, ketone, hydroxyl and ester groups, which contribute to adhesion and water compatibility of the polymer.
  • the oxidized polyethylenes are made by oxidation of polyethylenes (low density, medium density and high density types) with oxygen (typically provided as air) at elevated temperatures. Oxidized polyethylenes are semi-crystalline materials. These polymers are used for numerous applications. For example, these copolymers are used as additives in adhesives, coatings and inks.
  • the acid content in these polymers, or the polymers’ acid number is determined by method ASTM D-1386 method.
  • oxidized polyethylenes are commonly available in acid numbers from about 10 to 45 mg KOH/g.
  • the acidic groups in the polymers provides reactive sites for making water-based emulsions.
  • the number average molecular weight (Mn) of oxidized polyethylenes commonly ranges from 800 to 6,000 and their weight average molecular weight (Mw) commonly ranges from 1,500 to 20,000.
  • the molecular weight (for both Mn and Mw) of oxidized polyethylenes is determined by Gel Permeation Chromatography (GPC).
  • the density of the polymers commonly ranges from 0.85 to 1.00 g/cc as determined by method ASTM D-1505.
  • the Mettler drop point of the polymers ranges from 85°C to 145°C as determined by method ASTM D-3954.
  • the viscosity at 140°C of the polymers commonly ranges from 35 to 100,000 cps as determined by a Brookfield rotational viscometer.
  • the hardness of the polymers commonly ranges from less than 0.5 to 100 dmm as determined by method ASTM D-5.
  • Oxidized polyethylene polymer is commercially available from, for example, Honeywell International Inc. under the trade name A-C® 655.
  • A-C® 655 has the following specification: the acid number is 14 to 17 mg KOH/g; the hardness at 25°C is 2 to 3 dmm; the viscosity at 140°C (Brookfield) is 210 cps; the drop point (Mettler) is 107°C; and the density is 0.93 g/cc.
  • Another oxidized polyethylene polymer commercially available from Honeywell International Inc. is oxidized polyethylene sold under the trade name A-C® 656.
  • A-C® 656 has the following specification: the hardness at 25°C is 8 to 12 dmm; the drop point (Mettler) is 98°C; the density is 0.92 g/cc; the viscosity at 140°C (Brookfield) is 185 cps; and the acid number is 14 to 17 mg KOH/g.
  • Maleated polyolefins are well known to those skilled in the art, as is their manufacture. Maleated polyolefins contain polar groups in the polymer molecule. Maleated polyolefins can be made by grafting maleic anhydride to polyolefins with a peroxide. Maleated polyolefins are semi -crystalline materials. They are used for numerous applications. For example, these polymers are used as additives in adhesives, coatings and inks. Maleic anhydride contributes polarity, adhesion and lowers crystallinity. The maleic anhydride content in the polymers, or their saponification number or acid number, is determined by method ASTM D-1386 method.
  • Polymers with high saponification number contain a high content of maleic anhydride.
  • Commercial grades of maleated polyolefins are commonly available in saponification number from about 5 to 100.
  • the maleic anhydride group in the polymer provides reactive sites for making water-based emulsions of the polymer.
  • the number average molecular weight (Mn) of maleated polyolefins commonly ranges from 2,000 to 6,000 and their weight average molecular weight (Mw) commonly ranges from 5,000-20,000.
  • Mn and Mw weight average molecular weight (for both Mn and Mw) is determined by Gel Permeation Chromatography (GPC).
  • the density of the polymers commonly ranges from 0.90 to 1.00 g/cc as determined by method ASTM D-1505.
  • the Mettler drop point of the polymers commonly ranges from 100°C to 160°C, as determined by method ASTM D-3954.
  • the viscosity at 140°C of the maleated polyethylenes commonly ranges from 500 to 5,000 cps as determined by a Brookfield rotational viscometer.
  • the viscosity at 190°C of the maleated polypropylenes commonly ranges from 300 to 3,000 cps as determined by a Brookfield rotational viscometer.
  • the hardness values of the polymers range from less than 0.5 to 15 dmm as determined by method ASTM D-5.
  • Maleated polyolefin is commercially available from, for example, Honeywell International Inc.
  • Non-limiting examples of processes of making a combination, mixture, dispersion or emulsion of acrylate polymer or acrylate copolymer, rosin esters and the second polymer of the present disclosure are described in the Examples below.
  • the first polymer is present at a concentration of between about 50 weight % and about 99 weight % of the total dry weight of the composition; the tackifier is present at a concentration of between about zero weight % and about 40 weight % of the total dry weight of the composition; and the second polymer is present at a concentration of between about 1 weight % and about 17.5 weight % of the total dry weight of the composition.
  • the first polymer is present at a concentration of between about 59 weight % and about 65 weight % of the total dry weight of the composition.
  • the first polymer is present at a concentration of between about 65 weight % and about 75 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the first polymer is present at a concentration of between about 75 weight % and about 85 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the first polymer is present at a concentration of between about 85 weight % and about 99 weight % of the total dry weight of the composition. In some embodiments of the present disclosure, the tackifier is present at a concentration of between about zero weight % and about 10 weight % of the total dry weight of the composition.
  • the tackifier is present at a concentration of between about 10 weight % and about 20 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the tackifier is present at a concentration of between about 20 weight % and about 30 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the tackifier is present at a concentration of between about 30 weight % and about 40 weight % of the total dry weight of the composition. In some embodiments of the present disclosure, the second polymer is present at a concentration of between about 1 weight % and about 4 weight % of the total dry weight of the composition.
  • the second polymer is present at a concentration of between about 4 weight % and about 8 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of between about 8 weight % and about 12 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of between about 13 weight % and about 17.5 weight % of the total dry weight of the composition. In other embodiments of the present disclosure, the second polymer is present at a concentration of between about 17.5 weight % and about 30 weight % of the total dry weight of the composition.
  • the surface of a member to be adhered may be subjected to a suitable known or conventional surface treatment, e.g., a physical treatment such as a corona discharge treatment or a plasma treatment, a chemical treatment such as an undercoat treatment or a backside-treatment, or the like, prior to application of the adhesion compositions of the disclosure.
  • a suitable known or conventional surface treatment e.g., a physical treatment such as a corona discharge treatment or a plasma treatment, a chemical treatment such as an undercoat treatment or a backside-treatment, or the like.
  • wax refers to polymer products, such as those commercially available from Honeywell International Inc. under the following trade names: A-C® 5120, A-C® 645P, A-C® 655 and A-C® 656.
  • the disclosure also provides an article including a substrate and a top-coat composition disposed on the substrate.
  • the substrate may be any known in the art or described herein.
  • the substrate is wood, metal, plastic, etc.
  • the substrate may be a low surface energy substrate chosen from thermoplastic polyolefins, polyethylene terephthalate, polytetrafluoroethylene, polyvinyl fluoride, polypropylene, polyethylene, high density polyethylene, low density polyethylene, ethylene vinyl acetate, polyvinyl alcohol, acetal, acrylics, polyvinyl chloride, acrylonitrile butadiene styrene, polyurethane, epoxy, polyester, nylon, phenolics, polyimide, alkyd enamels, and combinations thereof.
  • the substrate is a low surface energy substrate chosen from high density polyethylene, low density polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and combinations thereof.
  • the substrate is polypropylene.
  • the substrate may be a thermoplastic polyolefin (TPO).
  • Polypropylene and TPOs can be used as a roofing membrane for painting signs, logos, on flat roofs.
  • adhesion to the polypropylene and/or TPO of the paint is not adequate.
  • various embodiments of this disclosure address this lack of adhesion and boost adhesion for roofing film membranes.
  • the substrate may be further defined as a roofing material, roofing film membrane, etc.
  • the top-coat composition has a first side disposed on and in direct contact with the substrate and a second side that is outermost and exposed to the environment.
  • the first side of the top-coat composition is disposed directly on the substrate such that there is no intermediate layer between them.
  • a corona treatment may be used to prepare the substrate for adhesion to the top-coat composition.
  • the first side of the top-coat composition is referred to as a bottom layer of the top-coat composition that is disposed on and in direct contact with a top layer of the substrate.
  • the second side of the top-coat composition is outermost, i.e., exposed to the environment. There is no other layer disposed on the second side of the top-coat composition.
  • the second side of the top-coat is described as a top layer of the article that is exposed to the environment.
  • the top-coat composition includes a first polymer, a second polymer, and water.
  • the top-coat composition may also include any one or more additives described herein or known in the art.
  • the first polymer may be any polymer described herein.
  • the second polymer may also be any polymer described herein.
  • the first polymer is selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinylacetate, vinyl acetate copolymers, ethylene-(meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene- (meth)acrylate copolymers, polyesters, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, casein, dextrin, starch, polysaccharides, copolymers of two or more thereof and combinations of two or more thereof; and combinations of any two or more thereof.
  • the first polymer is chosen from acrylic polymers, ethylene-vinyl acetate copolymers, and combinations thereof.
  • the first polymer may be an acrylic polymer.
  • the first polymer may alternatively be an ethylene-vinyl acetate copolymer. Each of these polymers may be as described above.
  • the top-coat composition is described as a commercially available paint, such as an interior or exterior house paint, commercial paint, etc. that includes the second polymer added thereto.
  • the paint is an exterior or commercial paint.
  • the first polymer may be a polymer found in any commercially available paint.
  • the commercially available paint may be supplied from companies including, but not limited to, Benjamin Moore, Sherwin-Williams, Valspar, Behr, PPG, Glidden, Olympic, Dutch Boy, etc.
  • the top-coat composition includes or is a commercially available paint to which the second polymer is added.
  • the second polymer is different than the first polymer and is selected from the group consisting of ethylene-acrylic acid copolymers, oxidized polyethylenes, ethyl ene-vinyl acetate copolymers, oxidized ethylene-vinyl acetate copolymers, maleated polyolefins, homopolymers of polyethylene, homopolymers of polypropylene, and combinations of any two or more thereof.
  • the terminology“different from” means that the first and second polymers are different on the molecular and molecular weight level. However, it is still contemplated that both the first and the second polymers may be of the same general type or genus. For example, both the first and second polymers could be ethylene-acrylic acid copolymers and yet still be different because they have different physical properties such as weight average molecular weight.
  • the second polymer is chosen from ethylene-acrylic acid copolymers, oxidized ethylene-vinyl acetate copolymers, maleated polyolefins, and combinations thereof.
  • the second polymer is an ethylene-acrylic acid copolymer.
  • the second polymer is an oxidized ethylene-vinyl acetate copolymer.
  • the second polymer is a maleated polyolefin.
  • the second polymer is a maleated polyethylene.
  • the second polymer may be a maleated polypropylene. Each of these polymers may be as described above.
  • the top-coat composition also includes water and can be described as a water borne coating or as an aqueous coating.
  • the amount of water may be any as described herein and/or as chosen by one of skill in the art.
  • the water is present in the top-coat composition in an amount of from 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, about 45 to about 50, or about 50, weight percent based on a total weight of the top-coat composition.
  • all values and ranges of values, both whole and fractional, between and including the aforementioned values are hereby expressly contemplated for use herein.
  • the top-coat composition may also include a surfactant.
  • the surfactant may be any as described herein.
  • a single surfactant or more than one surfactant may be utilized.
  • the surfactant may be utilized in any amount as described herein.
  • the top-coat composition has a solids content of greater than about 30, 35, 40, 45, or 50,% based on the total weight of the composition with a particle size of about 10 nm to about 2000 nm.
  • the solids content and/or particle size may be alternatively as any described herein.
  • the wet film has a thickness of about 25 to about 100, about 25 to about 75, about 25 to about 50, about 50 to about 100, or about 75 to about 100, microns, wherein 100 microns will typically dry to about 50 microns.
  • the substrate is corona-treated.
  • the corona treatment may be any known in the or described herein, such as in the Examples.
  • the article may exhibit improved retention (e.g. adhesion) of the top-coat to the substrate as compared to a top-coat that is free of the second polymer. This may be reported as a percentage of the top-coat that is removed or as a percentage of the top-coat that is retained.
  • the article may exhibit a retention (e.g. adhesion) of the top-coat of at least 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, 92, 96, or 100%.
  • the retention/adhesion describes an amount of the top-coat that remains adhered to the substrate after scoring, application of a tape, and then removal of the tape from the substrate.
  • the tackiness of the tape removes some portion of the top-coat from the scored substrate.
  • a retention of 100% refers to 100% of the top-coat remaining adhered to the substrate after removal of the tape.
  • test is run using a 5x5 grid such that 25 squares are etched or scribed into the top-coat. Therefore, in such a test, the removal of each square represents 4%.
  • all values and ranges of values, both whole and fractional, between and including the aforementioned values, are hereby expressly contemplated for use herein.
  • the retention/adhesion of the top-coat may be described/quantified as a percentage of the top-coat that is removed. For example, 100% removal would describe a scenario wherein all of the top-coat was removed and this is undesirable.
  • this disclosure provides various embodiments wherein the amount of the top coat removed from the substrate is 0, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, 92, or 96, %. This can be especially unexpected, surprising, and superior if a comparative article that includes a top-coat that is not of this disclosure experiences a high removal, e.g. 100%.
  • the retention/adhesion typically describes an amount of the top-coat that remains adhered to the substrate after scoring, application of a tape, and then removal of the tape from the substrate. Typically, the tackiness of the tape removes some portion of the top-coat from the scored substrate. In various non-limiting embodiments, all values and ranges of values, both whole and fractional, between and including the aforementioned values, are hereby expressly contemplated for use herein.
  • This disclosure also provides a method of forming the article.
  • This method includes the steps of providing the substrate, providing the top-coat composition, and disposing the top-coat composition on the substrate to form the article.
  • the top-coat composition may be cured using any mechanism known in the art. Typically, the test is run using a 5x5 grid such that 25 squares are etched or scribed into the top-coat. Therefore, in such a test, the removal of each square represents 4%.
  • This disclosure further provides a cured article that includes the substrate and a cured top-coat having a first side disposed on and in direct contact with said substrate and a second side that is outermost and exposed to the environment.
  • the top-coat comprises the cured product of the aforementioned first polymer.
  • This disclosure also provides a method of forming an article including the substrate and the top-coat, wherein the top-coat has a first side disposed on and in direct contact with the substrate and a second side that is outermost and exposed to the environment.
  • This method includes the step of providing the substrate and providing an aqueous coating comprising water and a first polymer selected from the group consisting of acrylic polymers, acrylonitrile butadiene, butyl rubber, cellulose acetate, cellulose butyrate, epoxy resins, ethylene-vinyl acetate copolymers, modified ethylene-vinylacetate, vinyl acetate copolymers, ethylene- (meth)acrylic acid ionomers, vinylidene chloride copolymers, ethylene-(meth)acrylate copolymers, polyesters, natural rubber, neoprene, phenolic polymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, styrene butadiene rubber, case
  • the method also includes the step of providing an emulsion of water, a surfactant, and a second polymer different than the first polymer and selected from the group consisting of ethylene-acrylic acid copolymers, oxidized polyethylenes, ethylene-vinyl acetate copolymers, oxidized ethylene-vinyl acetate copolymers, maleated polyolefins, homopolymers of polyethylene, homopolymers of polypropylene, and combinations of any two or more thereof.
  • the emulsion may be formed using any method known in the art or described herein. Similarly, the emulsion is not particularly limited and may be of any type, as recognized in the art.
  • the surfactant used in the emulsion may be any described herein.
  • the emulsion is described as a high solids - low surfactant emulsion that includes, for example, up to about 50 wt% solids and an amount of surfactant of zero or less than about 5 wt %.
  • the emulsion may be formed using more typical methods wherein the emulsion includes solids of about 25 to about 30 wt %, wherein a few weight percent of that value is surfactant.
  • the method also includes the step of combining the emulsion and the aqueous coating composition.
  • the emulsion is typically added to the aqueous coating.
  • the aqueous coating may be added to the emulsion.
  • the step of adding may occur in one step or may occur in several steps.
  • the method further includes the step of applying the combination of the emulsion and the aqueous coating composition to the substrate to form the top-coat having the first side disposed on and in direct contact with the substrate and the second side that is outermost and exposed to the environment.
  • the method may include the step of curing the top coat. The step of curing may be accomplished using any curing mechanism described herein or in the art.
  • a jacketed vessel was pre-heated to a temperature of 95-100°C. The temperature was controlled by an oil jacket, which contained oil at a temperature of about 115-120°C. 320 g of water was then added to the vessel and the temperature was adjusted to 96-99°C. Stirring (using Lightning RS500 saw tooth type blades) was commenced and a small amount potassium hydroxide was added and mixed with the water for 5 minutes. A small amount (less than about 2%) of the surfactant JPHOS® 1066 (commercially available from J1 Technologies Ltd., Manchester, UK), which contains an alkyl ether phosphate ester and phosphoric acid, was then added and mixed with the water for 5 minutes to form the aqueous phase of the emulsion.
  • JPHOS® 1066 commercially available from J1 Technologies Ltd., Manchester, UK
  • Ethylene-acrylic acid copolymer commercially available from Honeywell International Inc. under the trade name A-C® 5120, or a 25:75 mixture of said copolymer and the oxidized polyethylene polymer commercially available from Honeywell International Inc. under the trade name A-C® 656 was pre-melted with additives (5% w/w of Technical White Oil) at a temperature of about 110-115°C.
  • the material, once molten, was then mixed with low speed agitation.
  • the stirring speed was then increased to 960-1000 RPM and this molten wax phase was added, over a period of 3-5 minutes, to the center of the mixer containing the aqueous phase (see above).
  • the temperature was maintained at 97-99°C.
  • a pre-emulsion was thus formed at this stage and was mixed for another 5 minutes. 16 g of potassium hydroxide was added over a period of 1-2 minutes. At this stage a gradual increase in viscosity was observed as more potassium hydroxide was added. Mixing continued for another 5 minutes. The average particle size of the resulting emulsion was in the range of 0.3-0.6 microns. The pH of this high viscosity emulsion was then adjusted without affecting the particle size. Specifically, a small amount of 85% acetic acid in an amount of 1% of the total emulsion (v/v) was added to 60 g of hot water (temperature was in the range of 80-90°C) in a separate vessel and the resulting mixture was stirred.
  • This diluted acetic acid was then added to the viscous emulsion (see above) over a period of 1-2 minutes.
  • the emulsion became thinner and its viscosity was dramatically reduced.
  • the final product was initially cooled using the vessel jacket and then flash cooled in a sink or in-line cooler to 35°C. A small amount of biocide was added to the product once the temperature was below 35°C.
  • the product was then filtered through 200 microns filter to produce emulsified polymer particles corresponding to the second polymer b) of the present disclosure.
  • the final specification for the emulsion of the second polymer b) was as follows: the solids content was about 56%; the viscosity was 350 to 1500 cps (60 RPM Brookfield no.
  • the first polymer component (a) in the form of an acrylate polymer or copolymer emulsion was then provided, and the pH was adjusted to 7.5-8.0. and the dispersed tackifier resin added slowly over a period of 1-2 minutes with low speed stirring (200-400 RPM). After 5 minutes, the wax emulsion (see above) was added over a period of 1-2 minutes and the resulting mixture was stirred for 5 minutes. A wetting agent (LUMITIN® ISC (BASF)) was added and, optionally, water was also added to reach the desired viscosity. The adhesives were adjusted to 300-800 cps at 60 RPM Brookfield number 3 spindle 60 RPM. The different adhesives were then applied to labels according to procedures commonly known in the art and the labels were tested as set forth elsewhere herein.
  • the adhesive described in Example 2 was produced by combining 72 parts (by weight) of the acrylate copolymer commercially available from BASF Corporation, Charlotte, NC, USA, under the trade name ACRONAL® V215 with from about 14 parts to about 28 parts (by weight) of rosin ester resin commercially available from Eastman Chemical Company, Kingsport, TN, USA, under the trade name TACOLYNTM 3509 and 0 to about 14 parts (by weight) of ethylene-acrylic acid copolymer commercially available from Honeywell International Inc. under the trade name A- C® 5120 to result in a total of 100 parts. Amounts of these different components in the final adhesive can also be determined using commonly known techniques that are standard in the art. EXAMPLE 2: Testing of pressure-sensitive adhesive labels
  • Pressure-sensitive adhesive tapes containing different adhesives were tested for resistance to shear on stainless steel (Shear), loop tack to low density polyethylene (Tack Poly) and to stainless steel (Tack SS), and peel adhesion to card board (Peel Card) and to low density polyethylene (Peel Poly). Measurements were performed as described above, except that stainless steel was exchanged for low density polyethylene and card board as the adherent, as indicated in Figure 1.
  • Figure 1 shows adhesion properties on different substrates of pressure-sensitive adhesives containing about 72 weight % (of the total weight of the adhesive) of the acrylate copolymer commercially available from BASF Corporation, Charlotte, NC, USA, under the trade name ACRONAL® V215.
  • the pressure-sensitive adhesives contain rosin ester resin commercially available from Eastman Chemical Company, Kingsport, TN, USA, under the trade name TACOLYNTM 3509 and ethylene-acrylic acid copolymer commercially available from Honeywell International Inc. under the trade name A-C® 5120 in the indicated weight % (of the total weight of the adhesive).
  • the units of measurement are Newton per inch (about 2.5 cm; peel and tack) and hours (shear).
  • the order in which the test results regarding the different adhesives are depicted in the histogram corresponds to the order in which the different adhesives are mentioned in the figure legend below the histogram (left to right, top to bottom; this also applies to Figures 2-6).
  • Shear adhesion was determined based on the adhesion to stainless steel. Loop tack was determined based on the adhesion to low density polyethylene (Tack Poly) or stainless steel (Tack SS). Peel adhesion was determined based on the adhesion to low density polyethylene (Peel Poly) or card board (Peel Card).
  • Pressure-sensitive adhesives are also prepared that comprise the polymer products commercially available from Honeywell International Inc. under the trade names A-C® 645P and A-C® 655. These pressure-sensitive adhesives are manufactured in accordance with the information provided in Example 1 and are subjected to tests as those above.
  • Pressure-sensitive adhesives are also prepared that contain no rosin tackifier resin. These adhesives contain only the first polymer that is acrylate polymer or copolymer comprising polymerized monomers selected from the group consisting of acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, octyl acrylate, styrene, vinyl acetate and combinations of two or more thereof; and the second polymer selected from the group consisting of ethylene-acrylic acid copolymer, oxidized polyethylene, oxidized ethylene-vinyl acetate copolymer, maleated polyolefin and combinations of two or more thereof. These pressure-sensitive adhesives are manufactured in accordance with the information provided in Example 1 and are subjected to tests as those described above.
  • EXAMPLE 5 Heat Seal Adhesive
  • Sample A (control) is an ethylene-vinyl acetate emulsion (60% solids).
  • Sample B is a blend of 90% ethylene-vinyl acetate emulsion (Sample A) and 10% of low molecular weight ethylene-acrylic acid copolymer (A-C® 5120 from Honeywell) emulsion (53% solids).
  • the emulsions are coated on a 2-mil aluminum foil and dried in a forced air oven at 105°C to yield 30 gm of coating.
  • the coated foil is cut into small individual pieces (1 in x 6 in) which are then heat sealed to uncoated aluminum foil at 60 psi using a dwell time of 2 seconds and a temperature of 80°C. After conditioning for 24 hours at 72°F and a relative humidity of 50%, the laminates are delaminated with a tensile tester at a speed of 12 in/min. Peel force is measured and recorded. Sample B shows 25 % higher peel adhesion than sample A.
  • ACRONAL® V215 (BASF) is a popular water-based acrylic pressure sensitive adhesive, supplied at 69% solids, that is widely used in the production of self-adhesive labels and tapes.
  • the ACRONAL® V215 was combined with a 40% solids emulsion of an ethylene- acrylic acid (EAA) copolymer, having 15% acrylic acid by weight and a number average molecular weight of approximately 2000 Daltons, to give stable water-based adhesive compositions A, B, C and D. Samples were cast and dried in silicone rubber molds to yield dry adhesive sections suitable for rheological evaluation.
  • EAA ethylene- acrylic acid
  • Table 1 Viscoelastic Response of Unmodified and Modified Water-based Acrylic Pressure Sensitive Adhesives
  • MOWILITH® LDM1365 (Celanese) is an aqueous copolymer dispersion based on vinyl acetate, acrylic acid esters and ethylene (VAE) supplied at 60% solids. It is a widely used raw material in the compounding of adhesives for paper and packaging markets. MOWILITH® LDM1365 was combined with an ethylene-acrylic acid copolymer emulsion, a wetting agent and water to give water-based adhesive compositions X and Y at approximately 55% solids. The emulsion of the ethylene-acrylic acid copolymer was prepared at 53% solids and featured a copolymer with 15% acrylic acid by weight and a number average molecular weight of approximately 2000 Daltons.
  • the wetting agent JMULSE® 1444B3 (J1 Technologies), was included at 0.7% in the aqueous mixture.
  • Adhesive coatings were prepared on 25pm polyester film at a constant dry coat weight (of 24 gsm) for testing. The peel, loop tack, probe tack and shear characteristics of these coatings were evaluated according to well established test methods; see Table 2.
  • EXAMPLE 9 Adhesive Performance of a Tackified Water-Based Adhesive
  • An adhesive base was formulated with ACRONAL® V215 (BASF), a water-based acrylic pressure sensitive adhesive, EMULTROL® E177 (Concentrol Chemical Specialities), an aqueous dispersion of a rosin ester tackifier, and JMULSE® 1444B3 (J 1 Technologies), a wetting agent, to which an emulsion of an ethylene-acrylic acid copolymer was added.
  • the composition of the adhesive base was ACRONAL® V215 (100.0 parts by weight), EMEILTROL® E177 (40.5 parts by weight) and JMEILSE® 1444B3 (1.3 parts by weight).
  • the adhesive base was combined with an ethylene-acrylic acid copolymer emulsion prepared at 53% solids featuring a copolymer having 15% acrylic acid by weight and a number average molecular weight of approximately 2000 Daltons.
  • Pressure sensitive laminates were then prepared.
  • the wet adhesive was applied to a silicone coated release liner and dried in a laboratory oven to give a uniform dry adhesive coating (of 20 gsm), which was laminated with 80g face paper.
  • the resulting laminates were conditioned at 23 ⁇ 1 °C / 50 ⁇ 5% RH prior to testing according to well established procedures; see Table 4.
  • Adhesive HKJ23 (Adhesivos) is an aqueous acrylic copolymer dispersion supplied at about 53.5% solids. It is a widely used raw material in the compounding of adhesives for paper, polyolefin labels and decals market.
  • the Adhesivos HKJ23 was combined with an ethylene-acrylic acid copolymer emulsion and ethylene-acrylic acid copolymer (25%)/oxidized polyethylene (75%) dispersion to give water-based adhesive compositions at approximately 55% solids.
  • the emulsion of the ethylene-acrylic acid copolymer was prepared at 53% solids and featured a copolymer with 15% acrylic acid by weight and a number average molecular weight of approximately 2000 Daltons.
  • the emulsion of ethylene-acrylic acid copolymer (25 weight %) and oxidized polyethylene (75 weight %) was prepared at approximately 50% solids and its number average molecular weight was determined to be approximately 1,300.
  • the formulations are listed in Table 5A.
  • Adhesive coatings were prepared on 25 pm polyester film at a constant dry coat weight (of 24 gsm) for testing. Their peel, loop tack and shear characteristics were evaluated according to well established test methods; see Table 5B.
  • EXAMPLE 11 Process for preparation of EAA emulsion, A-C® 5120 Emulsion Formulation:
  • Emulsion vessel was preheated prior to the start of the process. Oil temperature was set at 120°C. The dispersion vessel was allowed to stabilize for 15 minutes after the addition of the hot water. Hot water at 95°C + was added to the Vessel the agitator blades were set running at 580 RPM. This was mixed for 15 Minutes. The first KOH was added and mixed for 5 minutes. JMULSE® 3527(H) was added and also mixed for 5 mins. The temperature at this stage was checked and was normally found to be 92-95°C. The wax/technical white oil was added in a steady stream at a temperature of 110-115°C over a period of 4-5 minutes.
  • the biocide was added to the final product. It was diluted 10/1 with water for the addition.
  • EXAMPLE 12 Process for preparation of PCP 002, A-C® 5656/ A-C® 5120 Emulsion
  • the 2 wax components (A-C® 656 and A-C® 5120) were preblended with technical white oil and kept in an oven at 110-115°C overnight.
  • the wax/oil was mixed prior to use in the formulation using a simple lab mixer for 5 Minutes.
  • the emulsion vessel was preheated prior to the start of the process. Oil temperature was set at 120°C.
  • the dispersion vessel was allowed to stabilize for 15 minutes after the addition of the hot water.
  • Hot water at 95°C + was added to the vessel the agitator blades were set running at 580 RPM. This was mixed for 15 minutes. The KOH was added and mixed for 5 minutes. The first JPHOS® 1066 was added and also mixed for 5 mins. The temperature at this stage was checked and was normally found to be 92-95°C. The wax/technical white oil was added in a steady stream at a temperature of 110-115°C over a period of 4-5 Minutes. At this stage the temperature rises and it was found to be important to adjust the heating oil to compensate for any rise or loss in temperature. For the addition of the wax, the mixer speed was raised to 960 RPM.
  • the product continued cooling to 45°C, and was then discharged.
  • the final emulsion was cooled in a sealed container to 30-35°C, filtered through 100 Mesh and placed into a sealed sample container.
  • the biocide was added to the final product. It was diluted 10/1 with water for the addition. If the product appears very viscous at this stage, extra water can be added to prevent skinning. If any skinning occurs during the final stages, the product can be refiltered.
  • EXAMPLE 13 Testing Emulsions of Example 11, Example 12, and A-C® polymer additives in Chimigraf flexographic ink formula
  • Formula A the control flexographic Ink formula from Chimigraf, was created by mixing 40 parts pigment (BLUE 206 HC CUAT from Chimigraf) and 60 parts of varnish (VARNISH COMPLEMENT 07 also from Chimigraf ) and agitating with a Speed Mixer for 2 minutes at 3000 rpm.
  • Formulas B - K (see Table below) were created by adding to Formula A an additional 5 to 25 parts of the emulsion of Example 11 (SF A-C® 5120 emulsion), emulsion of Example 12, or other A-C® polymer emulsion at 5 and 25 % dosage respectively, and speed mixing for 30 sec at 3000 rpm.
  • EXAMPLE 14 Adhesion (tape test) 1 hour and 4 hours after coating
  • EXAMPLE 15 Sutherland rub resistance before and after water immersion.
  • Sutherland rub test was performed using samples taped to the bed and a course white typing paper taped to a 4 pound test weight and cycled 400 times. Samples were air dried 24 hrs, then the starting sample was run and samples were placed separately in a bucket of 2°C water for 4 hours, and a bucket of ambient temperature water for 24 hours, and then tested. Samples were graded on a 0 to 5 scale for amount of ink transferred to paper, with 0 being no color and 5 being a heavy transfer of ink. Most samples were pale (2) to very faint (1) with a point added for serious streaks.
  • EXAMPLE 16 A Surfactant-Free Emulsion of an Ethylene Acrylic Acid Copolymer
  • Example 16 is an oil -in-water emulsion of a single ethylene acrylic acid copolymer formulated at 40% by weight of the copolymer.
  • the copolymer possesses 15% acrylic acid by weight and has a number average molecular weight of approximately 2000 Daltons.
  • a surfactant-free emulsion of the copolymer was simply created by partial conversion of the copolymer to its soap through the use of a base.
  • Ammonium hydroxide was used in this particular example; however, many other inorganic and organic bases are suitable.
  • the formulation of Example 16 is described in Table 6. Table 6: Emulsion Formulation of Example 16
  • the emulsion was prepared by combining ethylene acrylic acid copolymer (40.00 parts), 30% ammonium hydroxide solution (2.00 parts) and water (38.00 parts) in a reactor. The reactor was closed and the product temperature was raised to 95°C with continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. Separately water (20.00 parts) was heated to 95°C and then injected into the reactor.
  • the product was cooled to room temperature with continuous mixing.
  • the resulting product had a pH of 8.7, had a Brookfield viscosity of 220 cp, and showed a narrow particle size distribution centered at 0.2 pm.
  • EXAMPLE 17 A Surfactant-Free Emulsion of a Mixture of Ethylene Acrylic Acid Copolymers
  • Example 17 is an oil-in-water emulsion of a mixture of ethylene acrylic acid copolymers formulated at 35% by weight of the copolymers.
  • the first copolymer (EAA1) possesses 10% acrylic acid by weight and has a number average molecular weight of approximately 1100 Daltons.
  • the second copolymer (EAA2) possesses 20% acrylic acid by weight and has a number average molecular weight of approximately 2250 Daltons.
  • a surfactant-free emulsion of the copolymer was created by partial conversion of the copolymers to their soaps through the use of a base.
  • an organic base 2-amino-2-m ethyl- 1- propanol, was used, however many other inorganic and organic bases are suitable.
  • the formulation of Example 17 is described in Table 7.
  • the emulsion was prepared by combining the ethylene acrylic acid copolymer EAA1 (29.75 parts), ethylene acrylic acid copolymer EAA2 (5.25 parts), 2-amino-2-methyl-l- propanol (2.64 parts) and water (32.36 parts) were combined in a reactor.
  • EXAMPLE 18 An Emulsion of an Ethylene Acrylic Acid Copolymer
  • Example 18 is an oil-in-water emulsion of a single ethylene acrylic acid copolymer formulated at 52.75% by weight of the copolymer.
  • the copolymer possesses 15% acrylic acid by weight and has a number average molecular weight of approximately 2000 Daltons.
  • the emulsion is stabilized through a combination of the soap of the copolymer and an anionic surfactant.
  • the soap of the copolymer was created in-situ using potassium hydroxide, for which a 45% aqueous solution was used in the preparation to facilitate its use and accurate addition, while the anionic surfactant was JPHOS® 1066 (J1 Technologies, Manchester, UK).
  • the formulation of Example 18 is described in Table 8.
  • the emulsion was prepared by combining the ethylene acrylic acid copolymer (52.75 parts) and water (28.50 parts) were combined in a reactor. The reactor was closed and the product temperature was raised to 110°C with continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes.
  • the resulting product had a pH of 7.9, had a Brookfield viscosity of 3000 cp, and displayed a narrow particle size distribution centered at 0.2 pm.
  • EXAMPLE 19 An Emulsion of a Mixture of an Ethylene Acrylic Acid Copolymer and a Mineral Oil
  • Example 19 is an oil-in-water emulsion of an ethylene acrylic acid copolymer and a mineral oil formulated at 49.90% by weight of the copolymer and 2.85% by weight of the oil.
  • the copolymer possesses 15% acrylic acid by weight and has a number average molecular weight of approximately 2000 Daltons.
  • the selected mineral oil was SIPMED® 15 (SIP, London, UK). The emulsion is stabilized through a combination of the soap of the copolymer and an anionic surfactant.
  • the soap of the copolymer was created in-situ using potassium hydroxide, for which a 45% aqueous solution was used in the preparation to facilitate its use and accurate addition, while the anionic surfactant was JPHOS® 1066 (J1 Technologies, Manchester, UK).
  • the formulation of Example 19 is described in Table 9.
  • the emulsion was prepared by combining the ethylene acrylic acid copolymer (49.90 parts), SIPMED® 15 (2.85 parts) and water (28.50 parts) were combined in a reactor.
  • the product was cooled to room temperature with continuous mixing.
  • EXAMPLE 20 An Emulsion of a Mixture of Ethylene Acrylic Acid Copolymer and Oxidized Polyethylene Homopolymer
  • Example 20 is an oil-in-water emulsion of an ethylene acrylic acid copolymer and an oxidized polyethylene homopolymer. It was formulated at 10.73% by weight of the copolymer, 32.17% by weight of the oxidized polyethylene and includes 3.23% by weight of a mineral oil. The copolymer possesses 15% acrylic acid by weight and has a number average molecular weight of approximately 2000 Daltons. The oxidized polyethylene has a number average molecular weight of approximately 1200 Daltons and an acid number of 15 mg KOH/g. The selected mineral oil was SIPMED® 15 (SIP, London, UK). The emulsion is stabilized through a combination of the soap of the copolymer and an anionic surfactant.
  • the soap of the copolymer was created in-situ using potassium hydroxide, for which a 45% aqueous solution was used in the preparation to facilitate its use and accurate addition, while the anionic surfactant was JPHOS® 1066 (J1 Technologies, Manchester, UK).
  • a wetting agent and a biocide are also included in the formulation.
  • the wetting agent was JMULSE® 1444B3 (J1 Technologies, Manchester, UK).
  • the biocide was ACTICIDE® MBS (Thor Specialities, Northwich, UK).
  • the formulation of Example 20 is described in Table 10.
  • the emulsion was prepared by combining the ethylene acrylic acid copolymer (10.73 parts), oxidized polyethylene homopolymer (32.17 parts), SIPMED® 15 (3.23 parts) and water (22.00 parts) were combined in a reactor. The reactor was closed and the product temperature increased to 110 °C with continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. An aliquot of the 45% potassium hydroxide solution (0.30 parts) was injected into the reactor. The JPHOS® 1066 (1.67 parts) was injected into the reactor.
  • the resulting product had a pH of 8.1, had a Brookfield viscosity of 800 cp, and showed a narrow particle size distribution centered at 0.2 pm.
  • EXAMPLE 21 An Emulsion of a Mixture of Ethylene Acrylic Acid Copolymer and Rosin Ester
  • Example 21 is an oil-in-water emulsion of an ethylene acrylic acid copolymer and a rosin ester formulated at 38.75% by weight of the copolymer and 12.95% by weight of the rosin ester.
  • the copolymer possesses 15% acrylic acid by weight and has a number average molecular weight of approximately 2000 Daltons.
  • the selected rosin ester was SYLVATAC® RE85 (Arizona Chemical, Almere, The Netherlands).
  • the emulsion is stabilized through a combination of the soap of the copolymer and an anionic surfactant.
  • the soap of the copolymer was created in-situ using potassium hydroxide, for which a 45% aqueous solution was used in the preparation to facilitate its use and accurate addition, while the anionic surfactant was JPHOS® 1066 (J1 Technologies, Manchester, UK).
  • the formulation of Example 21 is described in Table 11.
  • the emulsion was prepared by combining the ethylene acrylic acid copolymer (38.75 parts), SYLVATAC® RE85 (12.95 parts) and water (28.00 parts) were combined in a reactor.
  • the reactor was closed and the product temperature was raised to 110 °C with continuous high shear mixing. The product temperature and shear environment were maintained for 10 minutes. An aliquot of the 45% potassium hydroxide solution (0.50 parts) was injected into the reactor. The JPHOS® 1066 (3.10 parts) was injected into the reactor. The balance of the 45% potassium hydroxide solution (2.14 parts) was injected into the reactor. The product temperature and shear environment were maintained for 20 minutes. Separately a dilute acetic acid solution was prepared from water (14.46 parts) and glacial acetic acid (0.10 parts), and heated to 85 °C. The dilute acetic acid solution was then injected into the reactor.
  • the resulting product had a pH of 8.5, had a Brookfield viscosity of 1500 cp, and showed a narrow particle size distribution centered at 0.2 pm.
  • the polypropylene is commercially available from Film Tech.
  • PI is an example of a second polymer and is a maleated polypropylene that has about 25.6% solids and is made with an anionic surfactant. It has a Mettler Drop Point (ASTM D-3954) of about 141°C, a Hardness (ASTM D-5) of less than about 0.5 dmm, a density
  • P2 is an example of a second polymer and is a maleated polypropylene that has about 39% solids and is made with an non-ionic surfactant. It has a Mettler Drop Point (ASTM D-3954) of about 141°C, a Hardness (ASTM D-5) of less than about 0.5 dmm, a density (ASTM D-1505) of about 0.94 g/cc, a viscosity (Brookfield) of about 350 cps at 190°C, a Saponification number of about 87 mg KOH/g, a % MAH Bound of about 72%, and a Bound SAP # of about 63 mg KOH/g.
  • ASTM D-3954 Mettler Drop Point
  • ASTM D-5 Hardness
  • ASTM D-1505 density
  • Brookfield a viscosity
  • ASAP an acid number
  • ASAP an acid number
  • P5 is an example of a second polymer and is an ethylene acrylic acid copolymer emulsion that has about 40% solids. It has a viscosity (Brookfield) of about 100 cps at 25 °C and a pH of about 8.
  • P6 is an example of a second polymer and is an ethylene-acrylic acid copolymer that has about 40% solids. It has a Drop Pt. of about 92°C, a Hardness at 25°C of about 7 dmm, a Density of about 0.93 g/ml, a Viscosity of about 1100 cps at 140°C, and an Acid No. of about 135 mg KOH/g.
  • P7 is an example of a second polymer and is an ethylene-acrylic acid copolymer that has about 40% solids. It has a Drop Pt. of about 90°C, a Hardness at 25°C of about 10 dmm, a Density of about 0.93 g/ml, a Viscosity of about 1000 cps at 140°C, and an Acid No. of about 150 mg KOH/g.
  • P8 is an example of a second polymer and is an ethylene-acrylic acid copolymer that has about 40% solids. It has a Drop Pt. of about 76°C, a Hardness at 25°C of about 50 dmm, a Density of about 0.93 g/ml, a Viscosity of about 625 cps at 140°C, and an Acid No. of about 185 mg KOH/g.

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Abstract

L'invention concerne un article qui comprend un substrat et une couche de finition présentant une première face se situant sur le substrat et en contact direct avec celui-ci, et une seconde face se situant le plus à l'extérieur et exposée à l'environnement. La couche de finition comprend un premier polymère choisi parmi les polymères acryliques, l'acrylonitrile butadiène, le caoutchouc butyle, l'acétate de cellulose, le butyrate de cellulose, les résines époxy, les copolymères d' éthylène-acétate de vinyle, l'éthylène-vinylacétate modifié, les copolymères d'acétate de vinyle, les ionomères d'éthylène-acide (méth)acrylique, les copolymères de chlorure de vinylidène, les copolymères d'éthylène-(méth)acrylate, les polyesters, le caoutchouc naturel, le néoprène, les polymères phénoliques, les polyuréthanes, l'acétate de polyvinyle, l'alcool polyvinylique, le caoutchouc styrène-butadiène, la caséine, la dextrine, l'amidon, les polysaccharides, des copolymères et des combinaisons de deux quelconques ou davantage de ceux-ci ; et des combinaisons de deux quelconques ou davantage de ceux-ci, d'un second polymère différent du premier polymère et choisi parmi les copolymères d'éthylène-acide acrylique, les polyéthylènes oxydés, les copolymères d'éthylène-acétate de vinyle, les copolymères d'éthylène-acétate de vinyle oxydés, les polyoléfines maléatées, les homopolymères de polyéthylène, les homopolymères de polypropylène et des combinaisons de deux quelconques ou davantage de ceux-ci, et d'eau.
PCT/US2019/067974 2018-12-21 2019-12-20 Article comprenant une couche de finition à base d'eau WO2020132519A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1020300A1 (fr) * 1999-01-13 2000-07-19 Azon Corporation Matériau pour l'impression au jet d'encre préparé à partir d'une formulation aqueuse
US20130231428A1 (en) * 2007-12-06 2013-09-05 Retec F3 Technologies, Sec. Fast film formation water based barrier coating
US8716389B2 (en) * 2011-02-07 2014-05-06 Nulabel Technologies, Inc. Fluid activatable adhesives and fluids for activating same for use with liner-free labels
WO2015160939A1 (fr) * 2014-04-15 2015-10-22 Honeywell International Inc. Compositions adhésives aqueuses à haute performance et applications
US20180251655A1 (en) * 2017-03-01 2018-09-06 Avery Dennison Corporation Print receptive topcoat
US20180320018A1 (en) * 2013-12-13 2018-11-08 Linwood G. Koger Water Based Printable Coatings
US20190127594A1 (en) * 2012-02-08 2019-05-02 Honeywell International Inc. Article comprising a water-based top-coat

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855820A (en) * 1997-11-13 1999-01-05 E. I. Du Pont De Nemours And Company Water based thick film conductive compositions
ATE478115T1 (de) * 2003-05-22 2010-09-15 Unitika Ltd Wässrige polyolefinharzdispersion, herstellungsverfahren dafür und diese enthaltendes wasserbasis-beschichtungsmaterial
US7803865B2 (en) * 2003-08-25 2010-09-28 Dow Global Technologies Inc. Aqueous dispersion, its production method, and its use
TW200517426A (en) * 2003-08-25 2005-06-01 Dow Global Technologies Inc Aqueous dispersion, its production method, and its use
EP2552978B1 (fr) * 2010-03-31 2020-08-26 Allnex Netherlands B.V. Dispersion polymère hybride à base d'eau
US10160891B2 (en) * 2012-02-08 2018-12-25 Honeywell International Inc. High performance water-based tackified acrylic pressure sensitive adhesives
JP2013193324A (ja) * 2012-03-19 2013-09-30 Fujifilm Corp 画像記録方法及び画像記録物
JP6408788B2 (ja) * 2013-05-07 2018-10-17 ユニチカ株式会社 環状ポリオレフィン材料用塗工剤及び積層体
JPWO2015194612A1 (ja) * 2014-06-20 2017-04-20 住友化学株式会社 水性エマルション並びに塗膜、硬化物及び積層体
RU2690855C1 (ru) * 2015-11-03 2019-06-06 БАСФ Коатингс ГмбХ Краски на водной основе, включающие сшивающие полиуретановые связующие вещества и определенную композицию растворителей
JP6880877B2 (ja) * 2016-03-24 2021-06-02 東洋インキＳｃホールディングス株式会社 化粧板用水性インキ組成物、印刷物、および化粧板用積層体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1020300A1 (fr) * 1999-01-13 2000-07-19 Azon Corporation Matériau pour l'impression au jet d'encre préparé à partir d'une formulation aqueuse
US20130231428A1 (en) * 2007-12-06 2013-09-05 Retec F3 Technologies, Sec. Fast film formation water based barrier coating
US8716389B2 (en) * 2011-02-07 2014-05-06 Nulabel Technologies, Inc. Fluid activatable adhesives and fluids for activating same for use with liner-free labels
US20190127594A1 (en) * 2012-02-08 2019-05-02 Honeywell International Inc. Article comprising a water-based top-coat
US20180320018A1 (en) * 2013-12-13 2018-11-08 Linwood G. Koger Water Based Printable Coatings
WO2015160939A1 (fr) * 2014-04-15 2015-10-22 Honeywell International Inc. Compositions adhésives aqueuses à haute performance et applications
US20180251655A1 (en) * 2017-03-01 2018-09-06 Avery Dennison Corporation Print receptive topcoat

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