WO2003066512A1 - Dispositif de fermeture synthetique - Google Patents

Dispositif de fermeture synthetique Download PDF

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Publication number
WO2003066512A1
WO2003066512A1 PCT/AU2003/000127 AU0300127W WO03066512A1 WO 2003066512 A1 WO2003066512 A1 WO 2003066512A1 AU 0300127 W AU0300127 W AU 0300127W WO 03066512 A1 WO03066512 A1 WO 03066512A1
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WO
WIPO (PCT)
Prior art keywords
closure
adhesion promoter
blank
organo
styrene
Prior art date
Application number
PCT/AU2003/000127
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English (en)
Other versions
WO2003066512A8 (fr
Inventor
Lee Joy Russell
Pamela Maree Hoobin
Eustathios Petinakis
Anthony Peter Cerra
Alexander Bilyk
Sheng Li
Wojciech Stanislaw Gutowski
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Commonwealth Scientific And Industrial Research Organisation
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Publication date
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to AU2003202316A priority Critical patent/AU2003202316A1/en
Publication of WO2003066512A1 publication Critical patent/WO2003066512A1/fr
Publication of WO2003066512A8 publication Critical patent/WO2003066512A8/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • B65D39/0005—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
    • B65D39/0011—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece from natural or synthetic cork, e.g. for wine bottles or the like
    • 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
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-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
    • B05D7/54—No clear coat specified
    • 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
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • B05D3/08—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 flames
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2539/00—Details relating to closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • B65D2539/001—Details of closures arranged within necks or pouring opening or in discharge apertures, e.g. stoppers
    • B65D2539/008—Details of closures arranged within necks or pouring opening or in discharge apertures, e.g. stoppers with coatings or coverings
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to synthetic closures and, in particular, to synthetic closures for containers such as wine bottles having an opening forming a neck.
  • the invention also relates to the manufacture of such closures and to their use.
  • the invention further relates to precursors of the synthetic closures and to their manufacture.
  • Natural cork is widely used for sealing bottled liquids, such as wines.
  • natural cork of suitable quality is relatively expensive due to its limited availability. Natural cork can also cause bacterial degradation and tainting of wine.
  • attempts have been made to replace natural cork with synthetic materials A problem exists however in producing a synthetic material having suitable surface properties.
  • the closure is intended to seal a container (typically a bottle) but also to be removable with relative ease. If the frictional interaction between the cork surface and the material from which the vessel is made is too great, the closure will be difficult to remove. Thus, if the closure is a cork for a bottle, the cork would be difficult to remove using a corkscrew.
  • the present invention seeks to address these disadvantages associated with conventional synthetic closures.
  • the present invention seeks to provide a synthetic closure which exhibits and maintains suitable frictional properties when in contact with the inner surfaces of the neck of a container in which the closure is to be used, and which may therefore be removed from the container with relative ease, whilst at the same time performing an adequate sealing function.
  • the present invention also seeks to provide a synthetic closure which remains intact and which shows structural integrity during insertion into and extraction from a container with which the closure is used.
  • the container is typically a glass bottle, particularly a bottle for wine.
  • the invention provides:- a closure for removable insertion into a container having an opening forming a neck, the closure comprising: a closure blank comprising a cylindrical surface formed of a synthetic polymer for locating within the neck of the container; a surface coating layer on the cylindrical surface of the closure blank comprising a slip agent for providing lubrication during removal and insertion; and an adhesion promoter selected from the group consisting of compounds comprising at least four amine groups with at least two amine groups being selected from primary and secondary amine groups and organo-functional coupling agents, said adhesion promoter bonding the coating to the cylindrical surface of the closure blank.
  • the synthetic closure blank may be formed of a range of synthetic polymers.
  • the synthetic closure blank is preferably a thermoplastic elastomer and more preferably comprises a styrenic block copolymer or a polyolefin elastomer.
  • the closure blank will generally comprise a surface comprising functional groups reactive with the adhesion promoter.
  • the surface of the closure blank is preferably activated by oxidation.
  • Oxidation typically provides surface functional groups such as hydroxyl and carboxyl functional groups on surface of a synthetic polymer (even where the synthetic polymer otherwise consists mainly of hydrocarbons). We have found the presence of such groups significantly improves the bonding of adhesion promoter and slip coating performance of the closures of the invention.
  • the slip agent is a cross-linkable slip agent which is cured on the blank preferably after priming the blank with adhesion promoter.
  • the invention further provide a synthetic closure on which a portion of the surface is printed with a suitable ink to provide for example, a name, trade mark, logo or decorative feature.
  • the invention provides a method for forming the above described closure comprising: providing a closure blank comprising a cylindrical surface formed of a synthetic polymer; oxidizing at least part of the cylindrical surface of the closure blank; contacting the oxidized surface with an adhesion promoter to bind the adhesion promoter to the oxidized surface wherein the adhesion promoter is selected from the group consisting of polyamines comprising at least four amine groups with at least two amine groups being selected from primary amine groups and secondary amine groups and organo-functional coupling agents; and applying a coating comprising a cross-linkable slip agent to the closure blank wherein the adhesion promoter provides adhesion between the oxidized portions of the cylindrical surface of the closure blank and the slip coating.
  • the method may include a step of curing the slip coating preferably at ambient temperature.
  • the blank treated with an adhesion promoter composition may be coated with slip coating during a continuous or sequential process.
  • the slip coating may be applied subsequently for instance by another manufacturer. Blanks the surface of which have been oxidised and treated with an adhesion promoter composition are storage stable and this allows for greater flexibility as to when and by whom the slip coating is applied.
  • a portion of the blank surface can be printed on with a suitable ink to provide a name, trade mark, logo or decorative feature. Printing can be done after oxidation of the blank surface and either before or after application of the adhesion promoter.
  • the surface oxidation and treatment with adhesion promoter can be repeated following printing with a ink to achieve better adhesion of slip coating and over all performance of the synthetic closure.
  • thermo-curable or UV curable ink are thermo-curable or UV curable ink.
  • Preferable inks are food-contact approved ink such as vegetable ink.
  • synthetic closure is intended to embrace plugs, stoppers, corks and the like, which are used to seal containers.
  • the invention is primarily concerned with the provision of synthetic closures for removable insertion into the neck of bottles, such as wine bottles.
  • closure and “cork” may be used synonymously.
  • a first step at least a portion of the surface of a synthetic closure blank is oxidised.
  • This step and the subsequent steps of applying the adhesion promoter composition and slip coating do not alter the macroscopic shape of the blank.
  • the cylindrical surface of the blank is essentially the same shape as the final closure it is desired to produce.
  • the cylindrical surface of the closure blank generally conforms to the lumen defined by the neck of the container.
  • the adhesion promoter composition and slip coating are generally provided as layers on the blank and the thickness of these layers, and the desired dimensions of the final product, will be taken into account when sizing the blank.
  • the blank is typically cylindrical, that is, the cylindrical surface for insertion into the container forms the whole length of the blank.
  • the closure blank may include one or more non-cylindrical portions joined to the cylindrical surface portion for location in the neck of the container.
  • the blank takes on the kind of dimensions of a natural cork for such bottles used in sparkling or non-sparkling wine.
  • the blank is made of a solid or foamed polymeric material.
  • polymeric material as used herein, is meant homo-polymers, co-polymers, thermoplastic rubbers and their blends and alloys with other materials such as inorganic fillers, and matrix composites.
  • Suitable polymeric materials useful in the present invention for forming the closure blank include thermoplastic polymers.
  • suitable polymeric materials may include polyolef s such as low density polyethylene (LDPE), polypropylene (PP), high density polyethylene (HDPE), polyolefin made with metallocene catalyst, polyblends of polyolefms with other polymers or with inorganic fillers, copolymers of polystyrene, EVA and poly(meth)acrylate optionally in admixture wth polyolefms .
  • LDPE low density polyethylene
  • PP polypropylene
  • HDPE high density polyethylene
  • polyolefin made with metallocene catalyst
  • polyblends of polyolefms with other polymers or with inorganic fillers copolymers of polystyrene, EVA and poly(meth)acrylate optionally in admixture wth polyolefms .
  • the polymeric material is a thermoplastic elastomer selected from the group consisting of styrene block copolymers and polyolefin elastomers.
  • styrene block copolymers may be selected from the group consisting of styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene- ethylene-butylene copolymer, styrene-butadiene-styrene copolymer, styrene- isoprene copolymer, styrene-ethylene-propylene-styrene copolymer and styrene-ethylene-propylene copolymer.
  • SEBS styrene-ethylene-butylene-styrene
  • a useful commercially available DRND type styrene block copolymer is available under the trade name SEPTON from the company Kuraray.
  • Another useful commercially available polyolefin elastomer is available from DuPont Dow under the trade name Engage®.
  • the polymer blank may be made by conventional techniques such as by extrusion, co-extrusion or injection moulding.
  • the blank can be made as a monolithic object from one polymer or blend or as a multi-layer object from more than one polymer or blend.
  • the method of the invention typically involves a first step of oxidizing at least a portion of the cylindrical surface of the closure blank.
  • a first step of oxidizing at least a portion of the cylindrical surface of the closure blank In principle only that portion of the surface of the closure that in use will be in contact with the opening to be sealed need be provided with slip coating. It follows from this that only the corresponding surface of the blank to be provided with slip coating needs to be oxidised. Usually, however, for convenience, the entire surface of the blank is oxidised, and subsequently treated with adhesion promoter and coated with slip coating.
  • Any suitable chemical or physical method may be used to oxidise the surface of the blank.
  • Such techniques include corona discharge, flame treatment, non- depositing plasma treatment at low or atmospheric pressure, chemical oxidation, UV irradiation and/or excimer laser treatment in the presence of an oxidising atmosphere such as air, oxygen (02), ozone (03), carbon dioxide (CO 2 ), Helium (He), Argon (Ar), and/or mixtures of these gases.
  • an oxidising atmosphere such as air, oxygen (02), ozone (03), carbon dioxide (CO 2 ), Helium (He), Argon (Ar), and/or mixtures of these gases.
  • corona discharge and/or flame treatment are preferred.
  • Suitable corona discharge energies range from 0.1-5000 mJ/mm 2 but more preferably 10-80 mJ/mm 2 .
  • Corona discharge treatment may be carried out in the presence of the following atmospheres: air, oxygen (02), ozone (03), carbon dioxide (C0 2 ), Helium (He), Argon (Ar), and/or mixtures of these gases.
  • the range of suitable energy is 5-5000 Watts for 0.1 seconds to 30 minutes, but more preferably 20-60 Watts for 1 to 60 seconds.
  • Preferred gases for non-depositing plasma are oxygen, air, nitrogen, water vapour, carbon dioxide, argon and helium.
  • any known flame treatment may be used to initially oxidise at least part of the surface of the blank.
  • Any range for suitable parameters can be used for the flame treatment.
  • the typical range of parameters for flame treatment is as follows: excess oxygen (%) detectable after combustion from 0.1% to 5%, preferably from 0.8% to 2%; speed from 1 m/min to 200 m/min, preferably from 10m/min to 100m/mm; treatment distance from 2 mm to 100mm, preferably from 5mm to 50mm.
  • gases are suitable for flame treatment. These include natural gases, pure combustible gases such as methane, ethane, propane, hydrogen, or a mixture of different combustible gases.
  • the combustion mixture may include air, pure oxygen or oxygen-containing gases.
  • oxidation of at least part of the surface of the blank can be effected with any known, standard oxidation solutions, such as chromic acid, potassium chlorate-sulfuric acid mixtures, chlorate-perchloric acid mixtures, potassium permanganate-suifuric acid mixtures, nitric acid, sulfuric acid, peroxodisulphate solution in water, chromium trioxide, or a dichromate solution in water, chromium trioxide dissolved in phosphoric acid and aqueous sulphuric acid.
  • chromic acid potassium chlorate-sulfuric acid mixtures, chlorate-perchloric acid mixtures, potassium permanganate-suifuric acid mixtures, nitric acid, sulfuric acid, peroxodisulphate solution in water, chromium trioxide, or a dichromate solution in water, chromium trioxide dissolved in phosphoric acid and aqueous sulphuric acid.
  • the oxidation is preferably carried out by flame oxidation or corona discharge, and more preferably jet corona discharge for cylindrical synthetic closure.
  • a useful jet corona system is commercially available from ARCOJET.
  • Preferable treatment conditions for corona systems such as ARCOJET jet corona are: distance between the electrode to the surface ranging from 5 to 20 mm; line speed varying from 1 to 100m/min; air flow speed from 4 to 12 m/second and energy output from 20 to 10000 mJ/mm 2 .
  • the oxidised blank is preferably treated with an adhesion promoter prior to treatment with the slip agent.
  • the adhesion promoter composition facilitates bonding of the subsequently applied slip coating and ensures adhesion and more effective control of the pull out force required for the discharge of closure.
  • the adhesion promoter composition typically comprises one or more compounds selected from consisting of (a) compounds comprising at least four amine groups with at least two amine groups being selected from primary and secondary amine groups and (b) organo-functional coupling agents.
  • the oxidised blank is treated with (a) a polyamine compound which is reactive with the oxidised surface of the blank and which comprises at least four amine groups including at least two amine groups selected from primary and secondary amine groups.
  • the composition may additionally comprise (b) a cross-linking agent that is reactive with the polyamine. Reaction between the polyamine and the cross-linking agent results in formation of a crosslinked network grafted to the surface of the blank.
  • the polyamine compound may be any compound which contains four or more amine groups with at least two of these amine groups being selected from primary (-NH 2 R) and secondary (-NHR 2 ) amines, where each R is independently an organic group such as alkyl, aryl, vinyl, substituted alkyl, substituted aryl or substituted vinyl.
  • the polyamine compound may be a polymeric or non-polymeric compound.
  • the molecular weight of the polymeric compounds is usually is between 200 and 3000000 more preferably 200 and 1000000 and most preferably 200 to 750000.
  • the polyamine polymer may be a homopolymer derived from monomers such as ethylenimine, allylamine, vinylamine, 4-aminostyrene and aminated acrylate/methacrylate, or a copolymer derived from a combination of two or more of these monomers, or a copolymer containing at least one of the monomers with any other suitable monomer such ethylene, propylene, acrylate/methacrylate and ethylene oxide.
  • PEIs polyethylenimines
  • Non-polymeric compounds which may be used include linear and carbon cyclic multi-amine compounds. Examples of such compounds are triethylene tetramine, tris (2-aminoethyl)amine, tetraethylene pentamine, pentaethylene hexamine, benzene tetraminie.
  • the adhesion promoter may optionally comprise a crosslinking agent. Typically however an adhesion promoter free of crosslinker may be used to provide a suitable closure product.
  • the crosslinking agents are usually compounds that contain at least two functional groups, at least one of which is capable of reacting with an amino group of the polyamine compound so that a stable bond is formed between the polyamine compound and the crosslinking agent.
  • the other functional group of the crosslinking agent should be suitable so as to join at least two polyamine molecules by either reacting with an amino group of another polyamine molecule or by bond formation with the functional group of another crosslinking agent molecule or by reaction with a co-crosslinking compound which is defined as a compound capable of bond formation with at least two molecules of crosslinking agent.
  • Functional groups which are suitable for initial reaction with the polyamine group include epoxides, anhydrides, acid chlorides, sulfonyl chlorides, ketones, aldehydes, carboxylic acids, esters, isocyanates, vinyl groups susceptible to Michael addition reactions such as acrylate, methacrylate, acrylamide, alkyl halides and alkynes.
  • the other functional group, which is responsible for the final crosslinking step may be selected from silanes, epoxides, anhydrides, acid chlorides, sulfonyl chlorides, ketones, aldehydes, carboxylic acids, isocyanates, acrylate and methacrylate esters and alkyl halides.
  • the mass ratio of polyamine compound to crosslinking agent is 100:1 to 1:100 with about 10:1 to 1:10 being preferred.
  • crosslinker When a crosslinker is used the type and combination of functional groups on the crosslinking agent may be chosen to enable crosslinking to take place at the surface of the blank and minimise crosslinking before application.
  • the crosslinking reaction can be controlled by designing a system where either:
  • a reagent is used which inhibits crosslinking in solution but once the formulation is applied to the blank surface the inhibitor is removed;
  • the crosslinking agent is a functionalised silane which contains at least one organic functional group for reaction with the polyamine and a silane group which will condense with other silane groups upon addition of water, forming Si-0-Si bonds for crosslinking.
  • the crosslinking silane may be of formula X-Si-R 1 (R 2 ) 2l where
  • X is any organic group containing at least one group selected from epoxide, anhydride, acid chloride, chloroformate, ketone, aldehyde, carboxylic acid, isocyanate, acrylate or methacrylate ester, acrylamide and alkyl halide containing 3 to 60 carbon atoms;
  • R 1 is a group susceptible to hydrolysis such as an alkoxide containing 1 to
  • R 2 may independently also be a group susceptible to hydrolysis such those mentioned 30 above for R 1 , alternatively R 2 may be selected from alkyl, aryl, vinyl, substituted alkyl, substituted vinyl or substituted aryl group, and any combination of these groups containing 1 to 40 carbon atoms. R 2 may also be any organic group containing at least one group selected from epoxide, anhydride, acid chloride, chloroformate, ketone, aldehyde, carboxylic acid, isocyanate, acrylate and methacrylate ester, acrylamide and alkyl halide containing 3 to 60 carbon atoms.
  • the silane is of formula X-R 1 -
  • X is selected from methacryloxy, acryloxy, acetoxy, chloride, bromide, iodide, glycidoxy, carbomethoxy, 4-chlorosulfonylphenyl, isocyanate, chloroformate, carbochloride, 3,4-epoxycyclohexyl and ureido groups;
  • the crosslinking silanes may be used in any combination as well as in partially or fully hydrolysed states as expected after exposure to water. Also, one or more co-crosslinking silanes may be added to the polyamine-silane crosslinking formulation. It is not necessary for the co-crosslinking silane to directly attach itself to the polyamine compound as it will be incorporated into a grafted interphase during the crosslinking processes via Si-0-Si bonding with the crosslinking silane directly bonded to the polyamine compound.
  • the co- crosslinking silane is usually a compound that contains one or more silane groups and may be defined by the formula SiR 1 R 2 R 3 R 4 , where:
  • the crosslinking agent may contain aldehyde or ketone functional groups or combinations thereof which can polymerize by an aldol condensation process and the resulting oligomers or polymers can act as crosslinking agents for polyamine compounds.
  • Examples of such crosslinking agents are glutaraldehyde, methyl or ethyl-pyruvate, pyruvic aldehyde, methyl or ethyl . levunate.
  • the crosslinking agent may be derived from any combination of these compounds and the condensation reaction to form the crosslinking agent can occur on mixing with the polyamine compound or the crosslinking agent can be prepared prior to the addition of the polyamine compound using any known acid, base or metal catalyst suitable for aldol condensation reactions.
  • the crosslinking agent may incorporate a reactive methylol group.
  • Such agents may be obtained from the reaction of two or more molar equivalents of formaldehyde with one of the following: substituted phenol, melamine, urea, benzoguanamine, or glycouril.
  • Such crosslinking agents can be prepared and used with the aid of acid or base catalysts, which is well known in this field. [Ref Henk van Dijk in "The chemistry and Application of Amino Crosslinking Agents or Aminoplasts -.John Wiley and Sons 1999 and T Brukhart, P. Oberssi and P. K. T. Oldring, "The Chemistry and Application of Phenolic Resins or Phenoplasts, John Wiley and Sons", 1998].
  • the methylol crosslinking agents can be in monomer form, or self-condensed oligomer or polymer form.
  • the methylol crosslinking agent is added to a dilute solution of the polyamine compound ( ⁇ 5%).
  • the crosslinking agent may contain at least one oxirane and one (meth)acrylate group.
  • the acrylate and the oxirane groups can be linked by an organic group such as an alkyl, aryl, substituted alkyl or substituted aryl group.
  • the compound may contain multi- or poly(meth)acrylate and oxirane groups.
  • Compounds containing acrylate and oxirane groups are more preferable as the chemical reactivity of acrylate with amine is higher than oxirane, so polyamine-containing oxirane groups can be formulated and further crosslinked on the oxidized polymeric substrate surface.
  • Such compounds are, for example, obtained by reacting an epoxy compound such as those referred to above with a (meth)acrylic acid or by condensing a compound containing a (meth)acrylate functionality with hydroxyl or carboxylic groups with an epihalohydrin.
  • Specific examples include glycidylacrylate, glycidyl methacrylate, epoxy acrylate of bisphenol A, 2-hydroxy-3-(4-oxiranylmethoxy-butoxy)-propyl acrylate, 2- hydroxy-3-[4-[1 -methyl]-1 -(4-oxiranylmethoxyphenyl)-ethyl-phenoxy] propyl acrylate, aromatic epoxy polyacrylate such as EPON Resin 8021, 8101, 8111, 8121, and 8161 from Shell Chemical Company, Epoxyacrylate Ebecryl 3605 (from UCB).
  • the crosslinking agent may be a compound containing at least two (meth)acrylate groups.
  • the (meth)acrylate groups are linked by an organic moiety which may be an alkyl, aryl, substituted alkyl or substituted aryl.
  • Compounds containing one acrylate group and one or more methacrylate groups are preferred because the difference in the rate of reaction between acrylate and methacrylate with amines allows for a formulation with a long pot life. In a typical formulation initial reaction of the amine with the acrylate is fast whilst the reaction with methacrylate is slower therefore making the final crosslinking step in solution slower.
  • crosslinking agents include 2-(acryloxy)ethermethacrylate, ethoxylated bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, alkoxylated aliphatic di(meth)acrylate ester, tris(2-hydroxylethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol propoxylate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di- or tri(meth)acrylate methacrylate ester, di- or tri(meth)acrylate acrylate ester, aliphatic urethane (meth)acrylate, aromatic urethane (meth)acryl
  • Suitable crosslinking agent is compounds containing one or more halogens and one or more selected groups from oxirane, (meth)acrylate, aldehyde, isocyanate and anhydride.
  • the halogen(s) and the other group are usually linked by an organic moiety which can be an alkyl, aryl, substituted alkyl or substituted aryl group.
  • suitable compounds include epichlorohydnin, epibromohydrin, epiiodohydrin, 2-bromoethyl acrylate, 3- bromopropyl acrylate, 4-bromobutyl acrylate, 6-bromohexyl acrylate, 7- bromoheptyl acrylate, 8-bromooctyl acrylate, 9-bromononyl acrylate, 11- bromoundecyl acrylate, 12-bromododecyl acrylate, 2-chloroethyl acrylate, 2-(2- chloroethoxy) ethyl acrylate, 2-[2-(2-chloroethoxy)ethoxy]ethyl acrylate, 4- chlorobutyl acrylate, 2-chlorocyclohexyl acrylate, 10-chlorodecyl acrylate, 6- chlorohexyl acrylate, 3-chloro-2,2-dimethylpropyl acryl
  • halogen-containing crosslinking agents an inorganic acid, organic acid or a mixture of both can be added to the polyamine formulation to increase the pot life of the solution.
  • an organic acid is added to the polyamine formulation so that the pH is less than 6, if the formulation is required to be stored for more than one day.
  • Suitable include hydrochloric acid, formic acid, acetic acid and oxalic acid.
  • the crosslinking agent may alternatively contain one or more halohydrin group(s) and one other group selected from oxirane, (meth)acrylate and aldehyde.
  • halohydrin group(s) and the other group are usually linked by an organic moiety, which may be an alkyl, aryl, substituted alkyl or substituted aryl group.
  • Suitable compounds are adducts of epihalohydrin with (meth)acrylate, hydroxyl, (meth)acrylic acid compounds or adducts of epoxy compounds partially reacted with halogen hydride or epoxy acrylate compounds with halogen hydride.
  • Examples include 3-bromo-2-hydroxy propyl acrylate, 3- chloro-2-hydroxy propyl acrylate, 2-(3-chloro-2hydroxy)propoxy-ethyl acrylate, 2-(3-bromo-2-hydroxy)propoxy-ethyl acrylate, 3-(3-chloro-2-hydroxy)propoxy- propyl acrylate, 3-(3-bromo-2-hydroxy)propoxy-propyl acrylate, 4-(3-chloro-2- hydroxy)propoxy-butyl acrylate, 4-(3-bromo-2-hydroxy)propoxy-butyl acrylate ,2- (3-chloro-2-hydroxypropoxycarbonyl) ethyl acrylate, and 2-(3-bromo-2- hydroxypropoxycarbonyl)ethyl acrylate.
  • the crosslinking agent may contain at least two anhydride groups.
  • the anhydride groups may be linked by an alkyl, aryl, substituted alkyl or substituted aryl group.
  • the anhydride may be selected from pyromellitic dianhydnide, 7,4,5,8-Naphthalenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetra- carboxylic dianhydride.
  • Anhydride-containing crosslinking agents may also be polymeric materials such as maleic anhydride copolymers with ethylene, propylene or maleic anhydride grafted onto polymers.
  • These polymers can be homopolymers or copolymers made from many types of monomer units including ethylene, propylene, isoprene, butadiene, methylacrylate, ethylacrylate methacrylate and butylacrylate.
  • the polyamine and optionally crosslinking agent are typically used in solution.
  • Any suitable solvent or mixture of solvents can be used provided it is compatible with the polyamine and crosslinking agent.
  • a preferred solvent, particularly because of occupational safety and environmental considerations is water, particularly with polyethylenimine, although the solubility of the cnosslinking agent should also be considered.
  • the adhesion promoter can be a single compound or mixture of one or more polyamines with one or more coupling agents optionally with a crosslinking agent.
  • the concentration of the adhesion promoter compound(s) in solution is usually between 0.000001% to 50% by weight, preferably between 0.001% and 5% by weight with the most useful concentration range being 0.01% to 1% by weight.
  • the adhesion promoter comprises a polyethylenimine (PEI) compound which may be linear or branched with a molecular weight range of 200 to 750000.
  • PEI compounds include products sold under the trade names "Lupasol FC", “Lupasol WF” and “Lupasol PS” (BASF).
  • the polyamine and crosslinking agent are pre-mixed under suitable conditions. In this case suppression of crosslinking before application to the oxidised surface of the blank is essential. This can be achieved by preparing the polyamine crosslinking agent mixture as a dilute solution as is the case when using aldehyde crosslinking agents such as glutaraldehyde with polyethyleneimine.
  • Another way to prevent unwanted crosslinking is to use a crosslinking agent that requires an external input to proceed, for example, a chemical initiator or catalyst such as water for silane- based crosslinking agents or a physical input, for example heat for maleated anhydride crosslinking agents.
  • crosslinking can be controlled by varying the reactivity of functional groups for example by using a combination of relatively reactive acrylate functional groups with less reactive methacrylate or epoxide groups.
  • the extent of crosslinking in solution can also be minimised by mixing the polyamine and crosslinking agent just prior to contact with the oxidised polymeric surface.
  • the desired result may be achieved by step wise addition of the polyamine and the crosslinking agent.
  • This method is particularly suitable for crosslinking agents that rely on very reactive functional groups, such as acid chlorides or isocyanates.
  • the polyamine can be applied to the blank surface first and the crosslinking agent applied afterwards.
  • the adhesion promoter solution can be applied by many standard methods including spray coating, dipping, roll coating, meniscus coating, spin coating and gravure coating. Once the solution is applied the solvent can be evaporated off either under ambient conditions or at elevated temperature using an oven, infrared radiation or other common method. On the other hand excess solution can be removed by washing with clean water or another solvent or blown off using a high pressure gas such as compressed air.
  • the time taken between the contact of the grafting solution with the oxidised surface of the blank and drying is from 0,001 seconds to 4 hours.
  • an external physical field such as ultrasonication can be applied dipping to enhance the grafting of the polyamine.
  • suitable physical fields such as heat, IR or microwave can be used to enhance or initiate the crosslinking reaction of the polyamine.
  • the adhesion promoter preferably applied to the substrate surface at a rate of less than 2g of the total of active agent (ie polyamine, coupling agent and optionally crosslinker) per square metre of surface area. Generally the thickness of the adhesion promoter layer will be less than 3 microns.
  • the adhesion promoter may be applied from solution with a suitable solvent or vapour.
  • a suitable solvent or vapour any aqueous and/or organic solvent or a mixture of both may be used to prepare the reactive solutions so long as it does not attack the substrate and permits sufficient dissolution of the amine containing compound(s).
  • Preferred solvents used for preparing the solution are water, and alcohols (e.g. isopropyl alcohol, and ethanol).
  • the adhesion promoter is a single polyamine compound. However, a mixture of two or more such compounds may be used if desired.
  • the particularly preferable concentration of polyamine is between 0.000001% to 10% by weight, more preferably less than 1% by weight (most preferably 0.01 to 1%). It may be desirable in this embodiment to avoid excess application of polyamine on the surface or to employ a washing step to remove excess or unbonded polyamine compound. Excess of polyamine compound on the surface can act as a weakly bond layer so to reduce the adhesion between the blank and the slip coating.
  • the adhesion promoter may be applied at any suitable temperature from room temperature up to, and above the boiling point of these compounds. Preferably, the compounds are applied at 20 to 100°C.
  • a suitable static and/or high frequency alternating physical field is simultaneously applied to the adhesion promoter and/or to the substrate.
  • Use of the physical field simultaneously also allows a higher grafting efficiency achieved at the lower concentration of the adhesion promoter.
  • any one of the following fields may be used: ultrasonic, microwave, radio frequency, heat energy or a combination thereof
  • ultrasonic field and/or microwave energy is used.
  • the preferred frequency range of applied ultrasonic energy ranges between I to 500 kHz, more preferably between 10 to 50 kHz.
  • microwave energy is applied in the range of from 1GHz to 300GHz.
  • the adhesion promoter comprises a coupling agent
  • the preferred coupling agents are organo-functional silane, organo-zirconate, organo-titanate, organo- tin or organo-aluminate coupling agents.
  • these coupling agents may be applied from solution with a suitable solvent or vapour.
  • any aqueous and/or organic solvent or a mixture of both may be used to prepare the reactive solutions so long as it does not attack the substrate and permits sufficient dissolution of the amine containing compounds.
  • Preferred solvents used for preparing the solution are water, and alcohols (e.g. isopropyl alcohol, and ethanol).
  • an organo-functional silane When an organo-functional silane is used, it preferably has the general structure X a SiY b , where X is a non-hydrolyzable organo-functional alkyl group, Y is a hydrolysable group, a is an integer from 1 to 3, and b is 4-a.
  • the organo-functional silane is of the formula X a Si(OR)b where X is a non- hydrolysable organo-functional group bonded to silicon through a stable covalent bond, R is any suitable alkyl group, preferably methyl or ethyl, a is an integer from I to 3 and b is 4-a.
  • the silanol groups obtained after hydrolysis of the alkoxy groups may react with hydroxyl and/or other functional groups introduced onto the surface of the polymer.
  • the group X comprises a functional group selected from the group consisting of a primary or secondary amine alkyl or polyamino alkyl or an expoxyalkyl.
  • the alkyl (substituted alkyl) groups preferably comprise from 1-6 carbon atoms.
  • Preferable coupling agents are amino silane, expoxy silane, amino zirconate and amino titanate.
  • Specific examples are 3-aminopropyltrimethoxysilane, 3- aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyl- triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(6-aminohexyl)aminopropyl- trimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, 3-(m- aminophenoxy)propyltrimethoxysilane, aminopropylsilanetriol,5,6-epoxyhexyl- triethoxysilane, 2-(3,4-epoxycycl
  • silane compounds are commercially available from Dow Corning under trade name Silane Z6020, Z6026, Z6040 or from Witco under trade name of SILQUEST A-1130, A-2120, A-1100TM, A-1170, A-1100, Y-9669, A-186, CoatOSil® 1770, A-187TM, Y15078.
  • a slip coating is applied.
  • Treatment of the oxidised surface of the blank with an adhesion promoter composition as described above enhances the adhesion of the slip coating to the closure and significantly improves the economy and performance of slip agents.
  • the thickness of the slip coating is of the order of a molecular monolayer to a 100 ⁇ m, typically from 10 nm to 3 ⁇ m.
  • the composition of the slip coating will dictate the chemistry used to bond it to the oxidised surface of the blank and one skilled in the art will be able to determine suitable chemistries to employ for a give application.
  • slip coating The primary function of slip coating is to lubricate the cork to allow smooth insertion of closure into a container and extraction of closure without excess of force. Another important function of slip coating is to provide a suitable seal in a container and maintain the proper seal during storage.
  • a further optional function of the slip coating is to provide barrier layer to block or reduce the migration of small compound or processing additives from the closure blank to the content of the container to minimize the detrimental effect on the content, for example tainting the wine.
  • barrier layer to further reduce or block the diffusion of oxygen into the container to reduce the detrimental effect to the content in the container.
  • the slip coating will generally have a balance of physical and chemical properties such as mechanical strength, rigidity, elasticity, friction coefficient and optionally barrier property to meet the requirement.
  • lubricant such as silicone oil, paraffin, vaselin, fatty acid, fatty acid amide, bee wax are blended or adsorbed into natural or synthetic cork to facilitate the insertion and extraction of cork. While this group of lubricant are known they are not suitable for this application.
  • the preferred slip coating of this invention comprises polymers exhibiting molecular weight greater than 5000 or crosslinkable polymer or oligomer giving an immobilized and forming a non-fluid final coating with a tensile strength ranging from 0.4 to 8Mpa and elongation from 100 to 1000%.
  • Suitable polymer for the slip coating are silicone polymer, crosslinkable silicone polymer or oligomer, polyurethane, crosslinkable urethane polymer or oligomer, acrylic polymer, crosslinkable acrylic oligomer and polymer, fluorinated polymer.
  • the slip coating can be in the form of a solution of oligomer, solution of polymer or oligomer with a suitable solvent or in the form of an emulsion.
  • the slip coating can be dried or cured at room or elevated temperature and preferably at 20 to 100°C.
  • the preferable slip coating is a crosslinkable formulation of crosslinkable polymer or oligomer and more preferably, a crosslinkable polymer or oligomer of silicone.
  • the slip coating is a silicone polymer or oligomer that cures at room temperature under atmospheric humidity.
  • the polymer or oligomer may be derived from polymethyl siloxane oil and one or more inert fillers. Suitable materials may be made by the application or adaptation of known techniques or are commercially available, e.g. Silbione Dispersion CAF 70004 manufactured by Rhone-Poulenc Chimie.
  • the slip coating may be applied by spraying, brushing, dipping or barrelling (tumbling).
  • the preferred technique is barrelling where a batch of suitably primed blanks are tumbled in a barrel mixer whilst slip coating is introduced into the mixer. Tumbling results in slip coating being applied to the blanks.
  • the slip coating is air dried.
  • a typical application process for a batch of 1000 wine closures would involve 1.5 ml of slip coating (such as CAF 70004) with tumbling at 23 rpm for 15 minutes followed by air drying.
  • the thickness of the slip coating may be manipulated by varying the solid content and the volume of slip coating added, the number of blanks to be coated in the batch and the tumbling time and speed.
  • the invention is particularly useful for making synthetic corks for wine bottles.
  • the cylindrical surface of the closure blank may extend the full length of the closure or may form a portion of the closure.
  • the invention may be used to produce a closure which is intended to be repeatedly inserted and removed from a container.
  • the closure of the invention may comprise a portion having a cylindrical surface for insertion into the neck of a container and enlarged or flange portion which allows the closure to be removed by hand by a pulling and twisting manipulation. Such a closure may then be used to reseal the bottle for subsequent storage and is useful in closures for spirits fortified wines such as brandy and port.
  • the polymer substrate is a thermoplastic elastomer (standing for hydrogenated poly butadiene) obtained from KURARAY Co. LTD and is under the trade name "SEPTON", was moulded into a flat sheet with a thickness of 3 mm. Coupons of dimensions 49mm x 30mm x 3 mm were cut from the sheet.
  • the slip coating (CAF 70004) was evenly applied using a metal blade.
  • a single lap shear test assembly was made from two coupons with an overlap of 10 mm, held together with two metal clamps and allowed to dry overnight followed by exposure for 72 hours in 100% humidity at 40°C. The thickness of the slip coating between the two coupons was approximately 100 micrometers.
  • the lap shear strength (dry and after 7 days immersion in water at 40°C) was measured using a 5565 lnstron mechanical tester.
  • Jet corona is produced from an ARCOJET Corona Generator, type PG052. Corona treatment took place in air for 0.6 second at an energy level of 4l6mJ/mm 2 .
  • the adhesion promoter was dissolved in water.
  • the polyethelenimine compounds obtained from BASF under trade name of Lupasol.
  • Lupasol G35 has an average molecular weight of 2000
  • Lupasol PS has an average molecular weight of 750000.
  • Lupasol SC-86X is a polyethylenimine epichiorohydrin having a number average molecular weight of 5000.
  • Amino silane Z6020 and epoxy silane Z6040 were obtained from Dow Corning.
  • Amino Zirconate "TEAZ" and amino Titanate TEAT were obtained from H ⁇ LS.
  • the adhesion promoter was applied by spraying, followed by removal of any excess using an air knife and oven drying at 60°C for 5 minutes.
  • Adhesion strength between the polymer substrate and the slip coating was assessed under dry and wet conditions. For the dry condition, a lap shear test was carried out after the curing of slip coating was completed. For the wet condition, the assembly was further immersed in 40°C water for 7 days prior lap shear test was carried out.
  • Bottle closures were made from a thermoplastic elastomer SEBS from KURARAY CO. LTD by injection moulding and subjected to various surface treatments.
  • Slip coating CAF 70004 was applied on the closure surface by a tumbling method using a commercial tumbler running at 23rpm.
  • the dosage rate of CAF 70004 was 1 .5ml CAF 70004 per 1000 10 closures.
  • Corona treatment was carried out using an ARCOJET corona generator with an energy output of 936mJ/mm 2 .
  • a conveyer was used to achieve even corona treatment on the cylindric shape surface of wine closure.
  • the treatment speed was 8m/min and the exposure time to the corona discharge was 0.6 seconds.
  • the adhesion promoter used was 0.01% Lupasol G35 in aqueous solution and applied onto the corona treated surface by spraying. Excess Lupasol G35 solution was blown away using an air knife. The residence time between application of Lupasol G35 solution the air knife was about 5 seconds. The treated closure was then dried at 110°C for about 8 seconds.
  • Closures provided with slip coating were bottled and then pulled out according to common practice in the industry. The closure surface was checked and flaking of the slip coating assessed visually.
  • the surface treatments were: i) No treatment; ii) Corona treatment only; Corona treatment and 0.01% Lupasol G35.
  • Example 3 This example is intended to illustrate the variation in bond strength between an ink and a polymeric substrate. Printing of a name, logo or decorative feature is commonly found on wine corks. Surface treatment must provide adequate adhesion to suitable ink to allow synthetic closure to be partially printed.
  • Polymer coupons of Example 1 were treated as follow: i) No treatment; ii) Corona treatment as Example I Hi) Corona treatment as ii) and treatment with an adhesion promoter.
  • a thin layer of vegetable ink (Sheetfed offset ink from Weberiink (GmbH) was coated on the treated polymeric surface using an ink applicator (Mickle Laboratory Engineering) and dried. The thickness of the ink was approximately 20 micrometers. Slip coating (CAF 70004) was then applied on the surface of polymeric coupon. Single lap shear assembly was made and tested as described in Example I. Results from the test were summarized in following table.
  • adhesion promoter defined in this invention also improves of the adhesion of ink to the closure blank.
  • the closure blank following surface oxidation and application of adhesion promoter can be therefore partially printed with a name, logo or decoration feature and then is bonded adequately with the slip coating.
  • Polymeric coupons were cleaned and corona treated as Example I then 30 % of surface was coated with vegetable ink in a pattern of five lines of width of 1 mm and apart from each other 5 mm. After drying, the surface was treated as following: i) No treatment; ii) Corona treatment as Example I iii) Corona treatment as ii) and treatment with an adhesion promoter

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
  • Closures For Containers (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)

Abstract

L'invention a trait à un dispositif de fermeture pouvant être inséré de manière amovible dans un récipient comportant une ouverture formant un goulot, ainsi qu'à un procédé de formation d'un tel dispositif de fermeture, lequel consiste à appliquer une couche de revêtement de surface sur une découpe de fermeture. Le revêtement contient un agent glissant conçu pour assurer une lubrification lors de l'extraction et de l'insertion du dispositif de fermeture. Le dispositif de fermeture comprend également un promoteur d'adhérence sélectionné parmi (a) des composés renfermant au moins quatre groupes amine, au moins deux groupes amine étant sélectionnés parmi des groupes amine primaires et secondaires, et (b) des agents de couplage organo-fonctionnels. Le promoteur d'adhérence fait adhérer le revêtement glissant à la surface cylindrique de la découpe de fermeture.
PCT/AU2003/000127 2002-02-08 2003-02-07 Dispositif de fermeture synthetique WO2003066512A1 (fr)

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FR2954329A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface elastomere d'un dispositif de distribution de produit fluide.
FR2954330A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954327A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954326A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954328A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
EP2608955A4 (fr) * 2010-08-25 2015-07-22 Dixie Consumer Products Llc Dispositif d'étanchéité amélioré pour gobelet en carton
WO2015196078A3 (fr) * 2014-06-20 2016-03-31 Nomacorc Llc Dispositif de femerture synthétique à composants multiples et son procédé de fabrication
WO2018015099A1 (fr) * 2016-07-18 2018-01-25 Unilever N.V. Procédé de modification des propriétés de distribution d'un récipient
US9896575B2 (en) 2012-06-11 2018-02-20 3M Innovative Properties Company Melt-processable compositions having silicone-containing polymeric process additive and synergist

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WO1995013883A1 (fr) * 1993-11-19 1995-05-26 Lermer Packaging Corp. Bouchons resineux synthetiques imprimes et leur procede de fabrication

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WO1994025513A1 (fr) * 1993-05-05 1994-11-10 Supreme Corq Bouchon moule pour recipients pour liquides
WO1995013883A1 (fr) * 1993-11-19 1995-05-26 Lermer Packaging Corp. Bouchons resineux synthetiques imprimes et leur procede de fabrication

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102612532A (zh) * 2009-12-23 2012-07-25 瓦卢瓦有限合伙公司 流体产品的分配设备的表面的处理方法
FR2954330A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954327A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954326A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
FR2954328A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
WO2011077049A1 (fr) * 2009-12-23 2011-06-30 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide.
WO2011077056A1 (fr) * 2009-12-23 2011-06-30 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide
FR2954329A1 (fr) * 2009-12-23 2011-06-24 Valois Sas Procede de traitement de surface elastomere d'un dispositif de distribution de produit fluide.
WO2011077055A1 (fr) * 2009-12-23 2011-06-30 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide
WO2011077052A1 (fr) * 2009-12-23 2011-06-30 Valois Sas Procede de traitement de surface elastomere d'un dispositif de distribution de produit fluide
WO2011077059A1 (fr) * 2009-12-23 2011-06-30 Valois Sas Procede de traitement de surface d'un dispositif de distribution de produit fluide
CN102639616A (zh) * 2009-12-23 2012-08-15 瓦卢瓦有限合伙公司 流体产品的分配设备的表面的处理方法
CN102639618A (zh) * 2009-12-23 2012-08-15 瓦卢瓦有限合伙公司 流体产品的分配设备的表面的处理方法
EP2608955A4 (fr) * 2010-08-25 2015-07-22 Dixie Consumer Products Llc Dispositif d'étanchéité amélioré pour gobelet en carton
US9114900B2 (en) 2010-08-25 2015-08-25 Dixie Consumer Products Llc Paper cup seal
US9896575B2 (en) 2012-06-11 2018-02-20 3M Innovative Properties Company Melt-processable compositions having silicone-containing polymeric process additive and synergist
WO2015196078A3 (fr) * 2014-06-20 2016-03-31 Nomacorc Llc Dispositif de femerture synthétique à composants multiples et son procédé de fabrication
US10286586B2 (en) 2014-06-20 2019-05-14 Vinventions Usa, Llc Multi-component synthetic closure and method of manufacture thereof
WO2018015099A1 (fr) * 2016-07-18 2018-01-25 Unilever N.V. Procédé de modification des propriétés de distribution d'un récipient
US10731016B2 (en) 2016-07-18 2020-08-04 Conopco, Inc. Method of modifying the dispensing properties of a container

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WO2003066512A8 (fr) 2003-09-25
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