KR20010033280A - Hydroxy-functional polyether laminates - Google Patents

Abstract

A laminate structure comprising at least one metal layer and at least one hydroxy-functional polyether, and optionally at least one organic polymer that is not a hydroxy-functional polyether. Such laminated structures are useful for the production of containers, such as aerosol containers and beverage containers.

Description

Hydroxy-functional polyether laminates

Metal-polymer laminates are known and are described, for example, in US Pat. Nos. 4,626,157, 4,423,823, 4,034,132, 4,686,152, 4,734,303, and 4,361,020. Polymers used in the manufacture of laminates include polyesters, polypropylenes, polyethylenes, polycarbonates, polyimides and blends thereof. Films made from such polymers suffer from inadequate adhesion to metals, cannot be stretched during metal forming due to the high orientation properties of the polymer film, and peel off during formation and / or end-use applications. Thin polyolefin-based films with polar comonomer adhesive layers provide good adhesion to metals and good elongation during metal lamination but result in laminate cuttability (coating “stringing”). ], And scratch resistance and end-use toughness are inadequate.

It is desirable to provide a polymer membrane having suitable toughness, wear resistance, thermal stability, ductility, formability, good barrier properties and chemical resistance to various chemicals.

In a first aspect, the invention relates to at least one metal layer and at least one hydroxy-functional polyether (hydroxy-functional polyether) layer, and optionally at least one organic polymer layer other than a hydroxy-functional polyether. It is a laminated structure containing.

In a second aspect, the invention relates to at least one metal layer and at least one hydroxy-functional polyether (hydroxy-functional polyether) layer, and optionally at least one organic polymer layer that is not a hydroxy-functional polyether. It is a container containing a laminated structure having.

Preferably, the hydroxy-functional polyether hydroxy-functional polyether used in the practice of the present invention to prepare the polymer layer (s) is:

(1) hydroxy-functional polyethers having repeating units of formula (I);

(2) amide- and hydroxymethyl-functional polyethers having repeating units of formula II;

(3) hydroxy-functional poly (ether sulfonamides) having repeat units of formula IIIa or IIIb;

(4) poly (hydroxy amide ethers) having repeating units independently represented by any one of formulas IVa, IVb or IVc;

(5) poly (hydroxy ester ethers) having repeat units of formula (V);

(6) poly (hydroxy amide ethers) having repeating units independently represented by any one of formulas VIa, VIb or VIc;

(7) poly (hydroxyamino ether) having a repeating unit of formula VII;

(8) hydroxy-functional polyethers having repeating units of formula (VIII).

In the above formula,

Each Ar independently represents a divalent aromatic residue, a substituted divalent aromatic residue or a heteroaromatic residue, or a combination of different divalent aromatic residues, substituted aromatic residues or heteroaromatic residues;

R is independently hydrogen or monovalent hydrocarbyl residues;

Ar ¹ is a divalent aromatic moiety or a combination of divalent aromatic moieties containing an amide or hydroxymethyl group;

Ar ² may be the same as or different from Ar, and independently represents a divalent aromatic residue, a substituted divalent aromatic residue or a heteroaromatic residue, or a combination of different divalent aromatic residues, substituted aromatic residues or heteroaromatic residues;

R ¹ is independently a major hydrocarbylene moiety, such as a divalent aromatic moiety, a substituted divalent aromatic moiety, a divalent heteroaromatic moiety, a divalent alkylene moiety, a divalent alkylene moiety or a divalent heteroalkyl Ren residues or a combination of such residues;

R ² is independently a monovalent hydrocarbyl residue;

A is an amine residue or a combination of different amine residues;

X is an amine, arylenedioxy, arylenedisulfonamido or arylenedicarboxy moiety or a combination of such moieties;

Ar ³ is a “cardo” residue, which is any one of the formulas:

, or

In the above formula,

Y is absent or is a covalent bond or a linking group wherein suitable linking groups include, for example, oxygen atoms, sulfur atoms, carbonyl atoms, sulfonyl groups or methylene groups or similar linkages;

n is an integer from 10 to 1000;

x is 0.01 to 1.0;

y is 0 to 0.5.

The term "main hydrocarbylene" means a divalent radical that is the main hydrocarbon, but contains small amounts of heteroatomic moieties such as oxygen, sulfur, imino, sulfonyl or sulfoxyl.

The hydroxy-functional polyethers of formula I can be prepared by reacting a combination of diglycidyl ether or diglycidyl ether with a dihydric phenol or a combination of dihydric phenols using the method described in US Pat. No. 5,164,472. Can be. In contrast, hydroxy-functional polyethers are prepared by journaling Applied Polymer Science, Volume by Reinking, Barnabeo and Hale. 7, page 2135 (1963), for example, by reaction with epihalohydrin.

Amide- and hydroxymethyl-functional polyethers of formula (II) are for example diglycidyl ethers, for example diglycidyl ethers of bisphenol A, pendant amido, N-substituted amido and / or hydroxy It can be prepared by reacting with diglycidyl phenol having oxyalkyl moieties such as 2,2-bis (4-hydroxyphenyl) acetamide and 3,5-dihydroxybenzamide. Such polyethers and their preparation are described in US Pat. Nos. 5,115,075 and 5,218,075.

The hydroxy-functional poly (ether sulfonamides) of formula III are for example diglycidyl ethers as described in US Pat. No. 5,149,768 for N, N'-dialkyl or N, N'-diaryldisulfonamides. It is prepared by polymerizing with.

Poly (hydroxy amide ethers) of formula IV are bis (hydroxyphenylamido) alkanes or arenes, or combinations of two or more of these compounds, such as N, N'-bis (3-hydroxyphenyl) adipamide Or N, N'-bis (3-hydroxyphenyl) glutaramide is contacted with epihalohydrin as described in US Pat. No. 5,134,218.

Poly (hydroxy ester ethers) of formula (V) are diglycidyl ethers of aliphatic or aromatic diacids, for example diglycidyl terephthalate, or diglycidyl ethers of dihydric phenols to aliphatic or aromatic diacids. For example by reacting with adipic acid or isophthalic acid. Such polyethers are described in US Pat. No. 5,171,820.

Poly (hydroxy amide ethers) of formula VI preferably contain N, N'-bis (hydroxyphenylamido) alkanes or arenes with diglycidyl ethers as described in US Pat. Nos. 5,089,588 and 5,143,998. It is prepared by contact.

Polyetheramines of formula (VII) are polymer backbones having at least one diglycidyl ether of dihydric phenol with an amine having two amine hydrogens and the amine moiety reacting with an epoxy moiety having an amine linkage, an ether linkage and a pendant hydroxyl moiety. It is prepared by contacting under conditions sufficient to form a. Such polyetheramines are described in US Pat. No. 5,275,853.

The hydroxy-functional polyethers of formula (VIII) can be used for example by converting one or more nucleophilic monomers into one or more diglycidyl ethers of cardo bisphenols, for example 9,9-bis (4-hydroxyphenyl) fluorene, Phenolphthalein, or phenolphthalimidine or substituted cardo bisphenol, such as substituted bis (hydroxyphenyl) fluorene, substituted phenolphthalein or substituted phenolphthalimidine, and the nucleophilic moiety of a nucleophilic monomer is an epoxy residue Prepared by reaction under conditions sufficient to form a polymer backbone having a pendant hydroxy moiety and an ether, imino, amino, sulfonamido or ester linkage, which is described in U.S. Patent Application No. 131,110 (October 1, 1993). One application).

Hydroxy-functional polyethers commercially available from Phenoxy Associates, Inc. are suitable for use in the present invention. Such hydroxy-functional polyethers are the condensation reaction products of bivalent polynuclearphenols such as bisphenol A with epihalohydrin, wherein Ar is isopropylidene diphenylene moiety. It has a repeating unit. Methods of making them are described in US Pat. No. 3,305,528.

Most preferably, the hydroxy-functional polyether used in the practice of the present invention is a polyetheramine of formula (VII).

Preferably, the molecular weight of the hydroxy-functional polyether is at least 20,000 and less than 100,000, preferably at least 30,000 and less than 80,000. Hydroxy-functional polyethers having low or excessive molecular weights are difficult to process and exhibit insufficient physical properties to form flexible films or suitable wet-outs and adhere to metal substrates.

In order to improve the chemical resistance, hardness, heat resistance or other performance properties of hydroxy-functional polyethers, by known copolymerization or graft copolymerization techniques or by ethylenically unsaturated dicarboxylic anhydrides or anhydride precursors, for example succinic acid or male Acid anhydrides; It may be modified by crosslinking with diisoxyanate, or formaldehyde, for example phenol-, urea- or melamine formaldehyde. This reaction (copolymerization, crosslinking) can be carried out by a reactive extraction method wherein the reactants are fed to the extruder using the conditions described in US Pat. No. 4,612,156 and react therein. This reaction can also be carried out after the film or laminate is formed by heat, moisture or ultraviolet-induced reactions.

Monolayer and multilayer films are conventional extrusion techniques such as feedback release, multimanifold or die coextrusion or a combination of the two, or slot-die casting or annular blown film extrusion; Extrusion coating to another substrate layer; Or from hydroxy-functional polyethers using solvent spray or solution casting. Solution casting is a well known method and is described, for example, in the Plastic Engineering Handbook of the Society of the Plastic Industry, Inc, 4th Edition, page 448. In addition, multiple plies of hydroxy-functional polyethers and / or other organic polymers can be attached to one another via conventional methods, such as hot-roll thermal lamination, to produce a multilayer structure. have. This lamination of a plurality of peeled layers or plies is particularly advantageous when the melt viscosity difference between the various layers is so great that co-extrusion of the layers is hindered. The films are subsequently uniaxially oriented in the machine or in the transverse direction, or biaxially in both machines and in the transverse direction to further improve their physical properties, e.g., increase in tensile strength and secant modulus and elongation. Can be reduced. This property change can be advantageous when stamping or cutting the polymer-metal laminate. In general, a multilayer film can be formed from the hydroxy-functional polyethers of the present invention by coextrusion of one or more hydroxy-functional polyethers and one or more organic polymers that are not hydroxy-functional polyethers. Such multilayered structures, whether formed through coextrusion, extrusion coating, liquid coating or multi-layer lamination, can be advantageously used to obtain complex properties not obtainable by monolayer films or multicomponent blends. One such example is the use of co-extrusion to bond the phenoxyether polymer to a metal substrate by adding an organic adhesive layer to hydroxy-functional polyethers that otherwise have poor adhesion. In the production of single and multilayer films, thermoplastic polyurethane (TPU), thermoplastic elastomer (TPE), polyester (PET), glycol-modified copolyester (PETG), polyolefin or other thermoplastics are hydroxy-functional. It may be mixed with the hydroxy-functional polyether at less than 50% by weight, preferably less than 30% by weight, based on the weight of the polyether layer. Such other polymers can be mixed into hydroxy-functional polyethers to reduce composition cost and modify physical, barrier or permeable or adhesive properties.

Additives such as fillers, pigments, stabilizers, impact modifiers, plasticizers, carbon blacks, conductive metal particles, abrasives and lubricating polymers can be incorporated into the hydroxy-functional polyether films. The method of introducing the additive is not important. The additive is conveniently added to the hydroxy-functional polyether before the film is made. If the polymer is made in solid form, the additive may be added before producing the film.

Preferably, the hydroxy-functional polyether film exhibits a final tensile strength of at least 7,000 psi, a yield elongation of 4 to 10%, a final elongation of 50 to 100% and a 2% secant modulus of at least 200,000 psi. The relatively high tensile strength, high module and low elongation of the film allows high speed die cutting without undesirable film stretching and stringing at the edges of the cut metal stack in the process where the film stack is used to make the aerosol valve mounting cups. Enables cutting and stamping into work. As used herein, the term "stringing" means "hair" caused by incomplete cutting of a partially attached polymeric coated fiber or metal laminate coating. The tough, extensible polymeric coating is drawn at the cutting edge of the metal where the partial cutting occurs, leaving a messy edge of the polymer or a thin, partially peeled polymer strip, hair, string or fiber. It is also preferred that the hydroxy-functional polyether exhibits an adhesion of at least 2.0 lb / in, preferably at least 3.0 lb / in to the metal substrate.

Monolayer films include hydroxy-functional polyethers.

Organic polymers that are not hydroxy-functional polyethers can be bonded to one or both sides of the hydroxy-functional polyether film to produce a multilayer film. Thus, the multilayer film can exist in the form of the following structure:

(1) A two-layer film comprising a first layer of hydroxy-functional polyether and a second layer of an organic polymer that is not a hydroxy-functional polyether.

(2) A three-layer film comprising a first outer layer of an organic polymer, a center layer of hydroxy-functional polyether and a second outer layer of an organic polymer that is the same or different from the organic polymer of the first outer layer.

(3) a first outer layer of a hydroxy-functional polyether, a central layer of an organic polymer that is not a hydroxy-functional polyether, and a second outer layer of an organic polymer that is the same or different than the organic polymer of the central layer 3-layer film.

(4) a hydroxy-functional polyether which is the same as or different from the first outer layer of the hydroxy-functional polyether, the central layer of the organic polymer other than the hydroxy-functional polyether and the hydroxy-functional polyether of the first outer layer A three-layer film comprising a second outer layer of functional polyether.

Organic polymers other than hydroxy-functional polyethers which can be used in the practice of the invention for producing multilayer films are crystalline thermoplastic polyesters such as polyethylene terephthalate (PET), amorphous thermoplastic polyesters such as Glycol modified polyesters (PETG); Polyamides, polyolefins and monovinyl aromatic monomer-based [polyolefin] styrenics; Carboxylic acid copolymers, and anhydride-modified polymers such as polyethylene grafted with maleic anhydride, ethylene-vinyl acetate and ethylene-butylacrylate-maleic anhydride terpolymers grafted with maleic anhydride.

Polyesters and methods for their preparation are known in the art and are referred to herein for the purposes of the present invention. Exemplary and non-limiting, see the Encyclopedia of Polymer Science and Engineering, 1988 revision, John Wiley & Sons, Volume 12, page 1-62.

Polyamides that can be used in the practice of the present invention include various grades of nylon, such as nylon 6, nylon 66 and nylon 12. Also included are polyamide copolymers of lower molecular weight and lower viscosity, which are used as hot-melt adhesives, are well known in the art and are commercially available from many suppliers.

Polyolefins that can be used in the practice of the present invention for producing multilayered laminate structures include propylene-polyethylene diene terpolymers as well as polypropylene, polyethylene and copolymers and blends thereof. Preferred polyolefins are polypropylene, linear high density polyethylene (HDPE), heterogeneously-branched linear low density polyethylene (LLDPE), for example DOWLEX ^™ polyethylene resin [trade name of The Dow Chemical Company], Homogeneously-branched ultra low density polyethylene (ULDPE) such as ATTANE ^™ ULDPE (trade name of The Dow Chemical Company); Homogeneously-branched linear ethylene / α-olefin copolymers, such as TAFMER ^™ (trade name of Mitsui PetroChemicals Company limited) and ESACT ^™ [Exxon Chemical Company) Trade name]; Homogeneously-branched substantially linear ethylene / α-olefin polymers such as AFFINITY ^™ (trade name of The Dow Chemical Company) and ENGAGE ^™ [du Pont Dow Elastomers LLC) Trade names of polyolefin elastomers, which may be prepared as disclosed in U.S. Patent Nos. 5,272,236 and 5,278,272; High pressure, free radically polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers such as PRIMACOR ^™ (trade name of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENE ^™ polymer (trade name of Exxon Chemical Company), and ELVAX ^™ [E.I. [Trade name of Du Pont de Nemours & Co.]. More preferred polyolefins have a density of 0.85 to 0.965 g / cm 3 (measured by ASTM D-792), a weight average molecular weight / number average molecular weight ratio (Mw / Mn) of 1.5 to 3.0, and a measured melt index of 0.01 to 100 g / 10 minutes Homogeneously-branched linear and substantially linear with (measured by ASTM D-1238 (190 / 2.16)) and I ₁₀ / I ₂ (measured by ASTM D-1238 (190/10)) of 6-20 Phosphorus ethylene copolymer.

Generally, high density polyethylene (HDPE) has a density of about 0.94 g / cm 3 (g / cc) (ASTM test method D-1505). HDPE is conventionally prepared using techniques similar to the preparation of linear low density polyethylene. Such techniques are described in US Pat. No. 2,825,721; 2,993,876; 2,993,876; 3,250,825 and 4,204,050. Preferred HDPE used in the practice of the present invention has a density of 0.94 to 0.99 g / cc and a melt index of 0.01 to 35 g / 10 minutes as measured by ASTM test method D-1238.

Monovinyl aromatic monomeric styrenes that can be used in the practice of the present invention include polystyrene, polymethylstyrene, styrene-acrylonitrile, styrene-maleic anhydride copolymers, styrene / methylstyrene or styrene / chlorostyrene copolymers. .

Other organic polymers that can be used in the practice of the present invention for producing multilayer films include polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,6-naphthalate and polyethylene 1,5-na. Phthalates, polytetramethylene 1,2-dioxybenzoate and copolymers of ethylene terephthalate and ethylene isophthalate.

The thickness of the monolayer or multilayer film depends on the number of factors including the purpose of use, the material stored in the container, the storage period prior to use and the particular composition used for each layer of the laminate structure.

In general, monolayer films have a thickness of 0.1 to 10.0 mils, preferably 0.2 to 5.0 mils, most preferably 0.4 to 1.0 mils. The multilayer film has an overall thickness of 0.1 to 10.0 mil, preferably 0.2 to 5.0 mil; The thickness of the hydroxy-functional polyether layer is 10 to 90%, preferably 20 to 80% of the total film thickness.

Metals that can be used in the practice of the present invention for producing polymer-metal or polymer-metal-polymer laminates are tinned steel (TPS), tin-free steel (TFS), electrochrome-coated steel (ECCS) , Galvanized steel, high strength low alloy steel, stainless steel, copper-plated steel, copper and aluminum. Preferred metals are tin plated steels and tin-free steels. Preferably, the metal is in the form of a flat sheet having two major surfaces.

For most metal packaging applications, the metal generally has a thickness of 3 to 20 mils, but the hydroxy-functional polyether film can be attached to any gauge metal. It is within the scope of the present invention to laminate hydroxy-functional polyether films onto thin metal foils, for example from 0.2 to 2 mils aluminum foil used for flexible packaging.

The polymer-metal or polymer-metal-polymer laminates of the present invention can be prepared by conventional lamination techniques. As is known in the art, certain lamination techniques include thermal lamination, i.e., heating the original melt activated adhesive film and thereby melt-bonding the metal substrate by heat and pressure; Or liquid coating and lamination, ie, peeled off adhesives, for example solvent-mediated or aqueous based adhesives, to the polymerizable film or metal substrate at the desired thickness, the liquid removed by a drying oven, the film and metal being heated and Bonding by pressure to attach the two layers together. In a manner similar to liquid coating, a hot-melt adhesive is melted and applied onto a film or metal by slot die coating or roll coating, and a molten hot-melt adhesive for tightly bonding the two layers of film and metal to the structure is applied. Use to combine pressure, then cool.

In general, a two-ply laminate comprising a polymer film layer and a metal layer can be prepared according to the present invention by contacting one of the major surfaces of the metal layer with the polymer film while simultaneously applying pressure at elevated temperatures. Similarly, a three-ply stack comprising a polymer film layer, a metal layer, and a polymer film layer is prepared by applying another polymer film layer that is the same or different from another polymer film layer on the remaining major surface of the metal layer.

The polymer-metal or polymer-metal-polymer laminate may have one of the following structures:

(a) A two-ply laminate comprising a first layer of hydroxy-functional polyether (hydroxy-functional polyether) and a second layer of metal.

(b) a three-ply stack comprising a first outer layer of an organic polymer that is not a hydroxy-functional polyether, a central layer of HPEE, and a second outer layer of metal.

(c) a three-ply stack comprising a first outer layer of hydroxy-functional polyether, a central layer that is not a hydroxy-functional polyether, and a second outer layer of metal.

(d) a three-ply laminate comprising a first outer layer of hydroxy-functional polyether, a central layer of metal and a second outer layer of an organic polymer that is not a hydroxy-functional polyether.

(e) a three-ply stack comprising a first outer layer of co-extruded hydroxy-functional polyether / PETG film, a central layer of metal and a second outer layer of an organic polymer other than hydroxy-functional polyether water.

Preferably, the organic polymer that is not a hydroxy-functional polyether is polypropylene.

In such a structure, the organic polymer that is not a hydroxy-functional polyether (hydroxy-functional polyether) can be a blend of two or more different organic polymers.

The polymer-metal or polymer-metal-polymer laminates of the present invention are suitable for use in the manufacture of three-dimensional metal structures, such as aerosol containers and various parts thereof, wherein the pressure sealing is used for crimped edges between two layers of steel sheets. It is obtained by forming together with the polymerizable layer imposed tightly on. In general, an aerosol container comprises a can body or wall which may be formed in one piece or may comprise a can body cylinder sealed at the bottom end by a distal element and at the top by a dome shaped cover element. The one-piece aerosol can body, or the dome-shaped cover element, has a spout that is closed by itself by a valve cup. The valve cup is usually deformed to fit the body. The polymer-metal or polymer-metal-polymer laminates of the present invention are suitable for use in the manufacture of aerosol valve mounting cups, aerosol can domes and bottom and can wall or body assemblies.

In addition, the polymer-metal or polymer-metal-polymer laminates of the present invention can be used to make other containers where chemical corrosion and pressure resistant sealing are required. In addition, in the manufacture of metal paint cans, the bottom of such cans can be stamped and formed from metal-polymer laminates and bonded to the cylinder face of the can with crimped sealing. The resulting seam is impermeable to solvents and other chemicals loaded into the vessel and remains as a leak-proof seal. The formation of such metal cans using components formed from the present metal-polymer laminate does not require the application of gasket material, for example isoprene rubber, separately along the periphery of the circular blank and at the same time curing it with solvent release. By using the coated metal according to the invention, the manufacturing process of the metal paint cans is streamlined, so that the efficiency is improved.

The polymer-metal laminate of the present invention may be deep drawn into shaped containers, for example beverage containers or food packaging containers or metal bulk packaging containers. The thermoplastic nature of the hydroxy-functional polyether film allows the polymerizable coating to be stretched and drawn sufficiently when the can structure is mechanically molded. Conventional thermoset coatings, such as cured epoxy coatings, are extremely brittle and brittle with respect to the stretching occurring during significant stretching of the metal substrate, for example during the deep-drawing of a one-piece can body.

In addition, large metal structures, such as indoor appliance covers, can be made from the polymer-metal laminates of the present invention. Indoor utensils such as refrigerators, washing machines, clothes dryers and dishwashers require an exterior and interior surface finish that is adherent to metal and provide moldability, durability, scratch and abrasion resistance, solvent resistance and aesthetic impressions. Should give. Hydroxy-functional polyether (hydroxy-functional polyether) film laminates generally replace the cured solvent-based primer and / or paint finishes used with pre-formed post-painting instrument covers. can do. The ductility and formability of the pigmented hydroxy-functional polyether film-metal laminate allows precoated wound steel to be molded into the instrument lid without requiring post-molding paint.

The following examples are for illustrative purposes and are not intended to limit the scope of the invention. Unless otherwise indicated, all parts and percentages are by weight.

Example 1

A monolayer 0.8 mil (20 μm) hydroxy-phenoxyether (phenoxy) film is prepared via conventional cast film extrusion using commercially available phenoxy resins, PaPhen PKFE from Phenoxy Associates, having a Tg of 100 ° C. and a molecular weight of 50,000. . The film is extruded at a melting temperature of 225 ° C., quenched on a chill-roll at 65 ° C., further cooled to 30 ° C. and wound up with a film roll. The 0.8 mil film is then thermally laminated separately using a continuous coil metal lamination method on a 10.5 mil tin plated steel preheated at a temperature of 204 ° C. and then quenched to room temperature using pressurized air cooling followed by a water cooled chill-roll. The phenoxy film exhibits good adhesion to the metal so that it cannot be peeled from the metal without bonding failure (tear) of the film at a peeling degree of more than 3.0 lb / in.

Example 2

Two layer coextruded 0.6 mil films can be prepared from glycol-modified copolyester (PETG) (PETG 6763 resin from Eastman Chemical Company) and phenoxy resin (PaPhen PKFE). Typically, a multilayer cast film line is used. PETG resin is extruded at a melting temperature of 225 ° C in one layer, but phenoxy resin is extruded at a melting temperature of 225 ° C into a second adjacent layer. The 0.6 mil film included 60% PETG layer and 40% phenoxy layer based on film thickness. The coextruded two-layer film is quenched on a chill-roll at 65 ° C., further cooled to 30 ° C. and wound up with a film roll. The 0.6 mil film was then thermally laminated onto a preheated 10.5 mil tin plated steel with a phenoxy layer bonded to the metal at a temperature of 204 ° C. (400 ° F.), followed by pressurized air cooling followed by a water cooled chill-roll Quench with. Phenoxy / PETG films cannot be peeled from the metal without disruptive tearing of such films.

Physical Properties of Examples 1 and 2 Films

film MD final tension (psi) TD final tensile (psi) MD% Yield Elongation (%) TD% Yield Elongation (%) MD% Final Elongation (%) TD% Final Elongation (%) MD 2% Split Modulus (psi) TD 2% Split Modulus (psi) MD elastomeric tear strength (g / mil) TD Elastomer Tear Strength (g / mil) Spencer Shock (g / mil) Example 1 10000 8000 9 6 170 200 277000 273000 12 13 295 Example 2 8700 5400 8 8 170 240 263000 251000 65 10 270

Example 3

The two-layer phenoxy / PETG film of Example 2 was thermally laminated at 204 ° C. on 10.5 mil tin plated steel in contact with the PETG layer preheated metal. Such films show good adhesion to metals and cannot be peeled off.

Example 4

Monolayer films of poly (hydroxy amino ether) (PHAE) resins are made in conventional cast film lines. PHAE resins are produced from the procedure described in US Pat. No. 5,275,853 after the reaction of diglycidyl ether (DGEBA) of bisphenol A with monoethanolamine (MEA) and have a molecular weight of 60,000 at a Tg of 70 ° C. The 0.5 mil film is extruded at a melt temperature of 210 ° C., quenched in a casting roll cooled at 65 ° C., then further cooled to 30 ° C., and rolled into a roll. This film is thermally laminated at 204 ° C. on 10.5 mil tin plated steel, 6 mil aluminum and 6 mil ECCS. In all three cases, the PHAE film shows good adhesion to the metal and cannot be peeled off from the metal.

Example 5

Two-layer coextruded films of PHAE and ethylene-acrylic acid (9% AA) are prepared via conventional cast film coextrusion. Both of these resins are extruded at 210 ° C. and quenched at 65 ° C., then further cooled to 30 ° C. and wound with a film roll. A 1.0 mil film was made with a layer ratio of 50% PHAE and 50% ethylene-acrylic acid (EAA). The film is then thermally laminated at 204 ° C. on preheated tinned steel to which the EAA layer of the coextruded film is in contact with and attached to the steel. Such films have an adhesion to metals of more than 3.0 lb / in and cannot be peeled off without breaking the film.

Example 6

A 0.6 mil biaxially oriented polyester (OPET) film is coated with a solvent based phenoxy solution (40% phenoxy solid in methyl-ethyl ketone, UCAR PKHS-40 from Phenoxy Associates). A wet liquid coating is applied to one side of the OPET film using a conventional liquid coater. The wet-coated film was then transferred to a multizone hot air impingement drying oven (zone temperature: 90 ° F. to 150 ° F., 32 ° C. to 65 ° C.) to evaporate the solvent, and 0.6 mil OPET film. Leave a 0.2 mil solid phenoxy layer on the phase. The 0.8 mil coated OPET film is then wound up in a roll. The film is then thermally laminated at 204 ° C. on preheated tin plated steel with a phenoxy layer attached to the metal surface using a coil metal lamination line. The hot laminate is then cooled to room temperature using pressurized air-cooled and water-cooled chill-rolls.

Example 7

The metal stacks of Examples 1, 2, 3, 4, 5 and 6 are drawn and molded into a 33 mm diameter x 12 mm cup using a Tinius Olsen Ductomatic BUP 200 metal forming press. A cup is produced having a thin film stack on the outer surface of such a cup and a thin film stack on the inner surface of the cup. These thin films show good adhesion to the formed metal without any film peeling observed.

Example 8

A co-extruded 7.2 mil polypropylene (PP) -hyperlinear low density polyethylene (ULLDPE) blend film was used on the opposite side of the metal to co-extrude a multilayered metal stack using the same phenoxy clock films as in Examples 1, 2, 3 and 4. It is produced from a phenoxy clock film while being laminated at the same time. Polypropylene film is a two-layer coextrusion main layer (85% of film gauge) and maleic anhydride grafted polyethylene adhesive layer (15% of film gauge) of 50% PP and 50% ULLDPE, which is taught in US Pat. No. 5,006,383 Are manufactured accordingly. A 7.2 mil PP film is laminated to the top surface of the preheated 10.5 mil tin plated steel and each of 0.5 to 0.8 mil of the phenoxy clock film of Examples 1, 2, 3 or 4 is laminated to the bottom surface of the steel. Thermal lamination is carried out at 204 ° C. by a continuous coil steel laminate coating method. After lamination, the double coated steel is cooled, rolled up, and cut to the desired width. The slit narrow web coils are stamped into a complex shaped 25 mm diameter aerosol valve mounting cup (AVMC) using a commercial continuous 14-station multi-die press. Each of the stacked structures shows good formability and drawability, and no peeling is observed. The aerosol valve mounting cup is then further converted to an aerosol valve assembly by adding a valve, actuator and stem assembly using a commercial valve assembly operation.

The present invention relates to metal-polymer laminates useful for the production of products such as beverage containers and aerosol containers.

Claims (22)

A laminate structure comprising at least one metal layer and at least one hydroxy-functional polyether layer, and optionally at least one organic polymer layer that is not a hydroxy-functional polyether. The laminate structure of claim 1 wherein the hydroxy-functional polyether layer is attached with or without a metal layer with or without an adhesive layer therebetween. The laminate structure of claim 1 comprising a metal layer and a hydroxy-functional polyether layer. The method of claim 1, wherein the first outer layer of the organic polymer other than the hydroxy-functional polyether, the center layer of the hydroxy-functional polyether and the second outer layer of the metal, and optionally, the first outer layer A laminate structure comprising an adhesive layer located between the center layer and / or between the second outer layer and the center layer. The method of claim 1, wherein the first outer layer of the hydroxy-functional polyether, the central layer of the organic polymer other than the hydroxy-functional polyether and the second outer layer of the metal, and optionally, the first outer layer and A laminate structure comprising an adhesive layer located between the center layer and / or between the second outer layer and the center layer. The method of claim 1, wherein the first outer layer of the hydroxy-functional polyether, the central layer of the metal and the second outer layer of the organic polymer other than the hydroxy-functional polyether, and, optionally, the first outer layer A laminate structure comprising an adhesive layer located between the center layer and / or between the second outer layer and the center layer. 7. The laminate structure of Claim 6 wherein the organic polymer that is not a hydroxy-functional polyether is polypropylene. The method of claim 1, wherein the first outer layer of the hydroxy-functional polyether, the central layer of the metal and the second outer layer of the hydroxy-functional polyether, and, optionally, between the first outer layer and the central layer And / or an adhesive layer located between the second outer layer and the center layer. The method of claim 1, wherein the first outer layer of the hydroxy-functional polyether or coextruded hydroxy-functional polyether / glycol-modified copolyester (PETG) film, the central layer of the metal and the polypropylene And a second outer layer, and optionally an adhesive layer located between the first outer layer and the center layer and / or between the second outer layer and the center layer. The laminate structure of claim 7 in the form of a three-dimensional metal structure. The laminate structure of claim 10 wherein the three-dimensional metal structure is an aerosol container, aerosol valve mounting cup, can bottom, can wall, beverage can, food packaging can, or metal bulk packaging container. The laminate structure of claim 8, wherein the laminate structure is in the form of a three-dimensional metal structure. The laminate structure of claim 12 wherein the three-dimensional metal structure is an aerosol container, aerosol valve mounting cup, can bottom, can wall, beverage can, food packaging can, or metal bulk packaging container. 10. The laminate structure of claim 9 in the form of a three-dimensional metal structure. The laminate structure of claim 14 wherein the three-dimensional metal structure is an aerosol container, aerosol valve mounting cup, can bottom, can wall, beverage can, food packaging can or metal bulk packaging container. 15. The layer of claim 14, wherein the polypropylene layer is laminated to the underside of the metal and the hydroxy-functional polyether or coextruded hydroxy-functional polyether / glycol-modified copolyester (PETG) film layer is metal Laminated structure laminated to the upper surface of the. The laminate structure of claim 7 in the form of a large metal structure. The laminate structure of claim 17, wherein the large metal structure is a refrigerator, a washing machine, a clothes dryer, or a dishwasher. The laminate structure of claim 8, wherein the laminate structure is in the form of a large metal structure. The laminate structure of claim 19 wherein the large metal structure is a refrigerator, a washing machine, a clothes dryer, or a dishwasher. 10. The laminate structure of Claim 9 in the form of a large metal structure. The laminate structure of claim 21 wherein the large metal structure is a refrigerator, a washing machine, a clothes dryer, or a dishwasher.