CA2136992A1 - Metal sheeting/polyurethane adhesive layer/polypropylene copolymer plastic film composite, process for its production, and its use for the production of packaging containers - Google Patents
Metal sheeting/polyurethane adhesive layer/polypropylene copolymer plastic film composite, process for its production, and its use for the production of packaging containersInfo
- Publication number
- CA2136992A1 CA2136992A1 CA002136992A CA2136992A CA2136992A1 CA 2136992 A1 CA2136992 A1 CA 2136992A1 CA 002136992 A CA002136992 A CA 002136992A CA 2136992 A CA2136992 A CA 2136992A CA 2136992 A1 CA2136992 A1 CA 2136992A1
- Authority
- CA
- Canada
- Prior art keywords
- plastic film
- polypropylene copolymer
- adhesive layer
- polyurethane adhesive
- metal sheeting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Abstract
Abstract:
Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite, process for its production, and its use for the production of packaging containers.
The present invention relates to metal sheet-ing/polyurethane adhesive layer/polypropylene copolymer plastic film composites in which the adhesive layer is obtained from a solvent-containing two-component poly-urethane adhesive.
The polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8% by weight of ethylene and/or further .alpha.-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution Mw:Mn in the range from 2 to 8 and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min.
Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite, process for its production, and its use for the production of packaging containers.
The present invention relates to metal sheet-ing/polyurethane adhesive layer/polypropylene copolymer plastic film composites in which the adhesive layer is obtained from a solvent-containing two-component poly-urethane adhesive.
The polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8% by weight of ethylene and/or further .alpha.-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution Mw:Mn in the range from 2 to 8 and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min.
Description
- 213~9~ ~
PAT 92 354 FILE. ~ttN TH!S ~r1r`~ L L' ~;
7~ TRANSL~ N
22.04.1993 BASF Lacke + Farben Aktiengesellschaft, Munster Metal sheeting/polyurethane adhe~ive layer/poly-propylene copolymer pla~tic film co~posite, proce~s for its production, and its use for the production of packagi~g container~
. ' The present invention relates to a metal sheeting/ polyurethane adhesive layer/polypropylene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive. The present inventionfurthermore relatec to a process for the production of the composite and to the use of the composite for the production of packaging containers.
In the productio~ of a can or a closure for use as a packaging material, in particular for the packag-ing of foodstuff B ~ metal sheeting made from tinplate, ;-chromated steel, such as ECCS (electrolytic chromium-coated steel~ and aluminum in sheet or tape form are -coated. The lacquer film acts as a protective coating, ~-;~25 on the one hand for protecting the metal against attack by the contents and consequent corrosion and on the other hand for preventing the contents being affected by corrosion products from the metal. Naturally, the lacquer film it~elf, for example through di~solved-out lacquer constituents, must not affect or impair the ~ 2 contents, neither during the sterilization of the contents carried out after filling nor during subsequent storage of the packaged contents, in parti-cular food~tuffs.
Furthermore, the lacquers must be built up in such a way that they withstand the mechanical stresses which occur during further conversion of the coated sheeting to cans or closures, for example during shaping, stamping, flanging, creasing etc. of the sheeting.
In addition, the high solvent emissions during drying of the lacquer film mean that precautions must be taken to keep these emissions and the consequent environmental pollution as low as pos~ible.
An advantageous process for the coating of metal sheeting employed, in particular, for the production of foodstuff packaging has proved to be the coating of metal sheeting with films. Thus, DE-A 3 128 641, for example, describes a process for the production of laminates for foodstuff packaging in which the metal sheeting and a thermoplastic resin film together with an adhesive based on a carboxyl-containing polyolefin arranged between these layers is heated to temperatures above the melting point of the adhesive and then cooled together with application of precsure~ producing the metal/plastic composite.
Furthermore, DE-A 2 912 023, GB-A-2,027,391 and EP-B-31 701 disclose laminates and foodstuff packaging ~ 3~992 :~:
containers, in particular bags, produced from these laminates.
A multiplicity of composites of metal foils with polyolefin or polypropylene films is known.
Examples of adhesion promoter~ employed are polar-modified polypropylenes, eg. polypropylenes grafted with carboxylic acids or carboxylic anhydrides. Com-posites of this type are described, for example, in EP-A-101 250 and EP-A-312 306. It is furthermore known that metal sheeting/polypropylene plastic film compo-sites can be produced using solvent-containing two-component polyurethane adhesives. However, the problem occurs in polypropylene plastic film/metal sheeting composites that the plastic films bonded to the metal tend toward stress whitening. Otherwise, polypropylene plastic films have greater chemicals resistance than polyethylene plastic films.
The present invention thus had the object, in particular, of developing polypropylene plastic film/metal sheeting composites which do not exhibit stress whitening after shaping to form a packaging container. In addition, the adhesion of the plastic film to the metal sheeting should of course be excel-lent. Naturally, the thermoplastic polypropylene film should pro~ect the metal in an optimum manner against attack by the contents and consequent corrosion and prevent the contents being affected by corrosion products from the metal. Furthermore, the plastic film itself, for example through dissolved-out constituents, should of course not affect or impair the contents, neither during sterilization of the contents carried out after filling nor during subsequent storage of the packaged goods, in particular foodstuffs. In addition, it should be ensured that the bonding of the plastic film to the metal sheeting can be carried out at conventional lamination rates at temperatures above the melting point of the polypropylene plastic.
Surprisingly, this object is achieved by a metal sheeting/polyurethane adhesive layer/polypropyl-ene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive. The composite is characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copoly-merization of from 1 to 8% by weight of ethylene and/or further ~-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution MW:Mn in the range from 2 to 8 and a melt flow index MFI 230C/2.16 kg in the range from 5 to 10 g/10 min, preferably in the range from 6 to 10 g/10 min.
The invention also relates to a process for the production of the composite and to the use of the coated metal sheeting for the production of packaging containers.
'~3~9~ :
The advantages of the metal sheeting/two-component polyurethane adhesive layer/polypropylene copolymer plastic film composites according to the invention are, in particular, that the composites have no tendency toward stress whitening after shaping to form a packaging container.
Metal sheeting which is suitable for the pro-duction of the coated metal sheeting according to the invention is sheeting having a thickness of from 0.04 to 1 mm made from tin-free steel, tinplate, aluminum and various iron al oys, which may have been provided with a passivation coating based on compounds of nickel, chromium and zinc. Depending on the applica-tion, metal thicknesses of greater than 1 mm are also possible.
The metal sheeting is coated with thermoplastic polypropylene plastic film, the adhesion of the film to the metal sheeting being accomplished by means of a polyurethane adhesive.
The thermoplastic polypropylenes used to produce the plastic film are random polypropylene copolymers in the form of a film. These may also be composite films (multilayer films) obtained, for example, by joint extrusion of the polypropylene random copolymers.~ Polypropylene films of this type are pro-duced by known processes (blow processes, chill-roll processes, etc.) from granules of the polypropylenes.
The polypropylene copolymer plastic film of the composite according to the invention fully or ~136992 essentiall~ comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8%
by weight of ethylene and/or further ~-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition. Examples of further ~-monoolefins with the exception of propylene are, for example, C4-to C12- ~-monoolefins, such as 1-butene, 4-methyl-1-pentene, 1-hexene, 1-n-octene, 1-n-decene and 1-n-dodecene.
The polypropylene copolymer plastic film of the composite according to the invention is particularly preferably produced from a propylene copolymer obtained exclusively from the abovementioned amounts of ethylene and propylene.
The polypropylene copolymers have a molecular weight distribution MW:Mn in the range from 2 to 8 and a melt flow index MFI 230C/2.16 kg in the range from 5 to 13 g/10 min, preferably in the range from 6 to 20 10 g/10 min (measured in accordance with DIN 53 735).
The copolymer can be prepared by the polymeri-zation process described in DE-A 37 30 022 using a Ziegler-Natta catalyst system. For example, they are prepared by the so-called gas-phase polymerization 25 process at temperatures of from 20 to 160C and at a pressure of from 1 to 100 bar. The molecular weights of the polymers can be regulated by generally known measures, for example by means of hydrogen as poly-merization regulator or by peroxidic degradation.
._.. .. .
.~: ~. : .
213~992 The plastic films of the composites according to the invention are preferably obtained from poly-propylene copolymers prepared by random copolymeriza-tion of from 2 to 4% by weight of ethylene and from 98 to 96% by weight of propylene, based on the total weight of the monomer composition, the random copoly~
mers having a molecular weight distribution MW:Mn in the range from 2 to 5, particularly preferably in the range from 3 to 4, and a melt flow index MFI
230C/2.16 kg in the range from 5 to 10 g/10 min, particularly preferably in the range from 7 to 9 g/10 min (measured in accordance with DIN 53 735).
The polypropylene copolymers used in accordance with the present invention for the production of the metal/plastic film composites have a melting range of from about 135C to about 150C (determined by DSC).
They are obtainable, for example, under the trads name Novolen~ 3225 MCX (BASF AG).
The plastic of the plastic film used in the composite according to the invention preferably fully comprises the polypropylene copolymer described above.
However, it is also possible within the scope of the invention to extrude mixtures of the copolymer described and small amounts of other thermoplastics, preferably polypropylenes, to give a plastic film which can be employed in the composite. It is furthermore possible to employ multilayer films of said propylene copolymers which are obtainable by coextrusion.
~,. ~,.,_. .. - - - - - -3 5 9 ~ 2 ~ he thermoplastic polypropylene plastic film of the composite according to the invention may also contain conventional additives, such as, for example, internal and external lubricants, antiblocking agents, stabilizers, antioxidants, pigments, crystallization assistants and the like. These additives are employed in the amounts necessary for preparation, processing, make-up and use, in the form of powders, dusts, beads or a concentrate which is incorporated directly into the polymer. Further details on the amounts convention-ally employed and examples of suitable additive~ are given, for example, in Gachter-MUller, Kunststoff-additive, Carl-Hanser Verlag.
It is particularly advantageous if the thermo-plastic polypropylene films of the composites containup to 0.5% by weight, based on the total weight of the film, of erucamide and/or oleamide as lubricant and up to 0.2% by weight, based on the total weight of the plastic film, of antiblocking agent, preferably silicon dioxide, and if desired, antioxidants and, if desired, further processing stabilizers and further additives.
Preferred antioxidants are phenol derivatives.
Further suitable additives are titanium dioxide, calcium carbonate, diatomaceou~ earth, metal stearates and primary and secondary fatty acid amides. Examples of the W stabilizers employed are W stabilizers of the HALS type.
The adhesive layer arranged between the poly-propylene copolymer plastic film and the metal sheeting ~_.. ,, .. .. , . . , . . , . , -'~ 9 2 g may likewise contain the abovementioned additives.
However, these are preferably incorporated into the polypropylene plastic film.
The adhesive layer arranged between the metal sheeting and the polypropylene copolymer plastic film is obtained from a two-component, solvent-containing polyurethane adhesive. Any suitable proce~s can be used to apply the adhesive to the metal sheeting. The two-component polyurethane adhesive is applied by application from solutions in organic solvents. The solutions generally have an adhesive content of from 5 to 80% by weight. The amount of adhesive applied is generally from about 1 to 15 g/m2 [sic] of area.
The two-component polyurethane adhesive com-prises an OH-containing component (I), for example polyester-polyols, polyether-polyols or low-molecular-weight polyols, and an isocyanate group-containing component (II). The two components are mixed with one another immediately before application to the substrate.
Component (I) of the 2-component adhesive preferably comprises polye~ter-polyols. These are pre-pared by esterifying dicarboxylic acids by means of excess diols or polyols.
The esterification proceeds at elevated tem-perature in solution or in the melt. Dicarboxylic acids and glycols give linear polyesters, while esterifica-tion in the presence of triols and/or higher-functional polyols gives polyesters with a certain degree of ~13~992 branching. The polyester-polyols are obtainable by reacting polycar~oxylic acids or esterification-capable derivatives thereof, if desired together with mono-carboxylic acids, polyols, if desired together with monools, and, if desired, further modifying components.
Examples of suitable polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicar-boxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydro-phthalic acid, endomethylenetetrahydrophthalic acid, cyclohexanetetracarboxylic acid and cyclobutanetetra-carboxylic acid, Also suitable are the esterifiable derivatives of the abovementioned polycarboxylic acids, such as, for example, their monoesters or polyesters with aliphatic alcohols having 1 to 4 carbon atoms or hydroxy alcohols having 1 to 4 carbon atoms. In addition, the anhydrides of the abovementioned acids, if they exist, may also be employed.
If desired, monocarboxylic acids may also be employed together with the polycarboxylic acids;
examples are benzoic acid, tert-butylbenzoic acid, lauric acid, isononanoic acid and fatty acids of naturally occurring oils. The preferred monocarboxylic acid employed i~ isononanoic acid.
~1~6992 Suitable alcohol components for the preparation of the polyesters are polyhydric alcohols, such as ethylene glycol, propanediols, butanediols, hexanediols, neopentyl glycol, diethylene glycol, cyclohexanediol, cycloh~xanedimethanol, trimethyl-pentanediol, ethylbutylpropanediol, ditrimethylol-propane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, tris-hydoxyethyl [sic] isocyanurate, polyethylene glycol, polypropylene glycol, if desired together with monohydric alcohol~, such as, for example, butanol, octanol, lauryl alcohol, ethoxylated or propxylated [sic] phenols.
Suitable modifying components are polyiso-cyanates and/or diepoxide compounds, if desired alsomonoiQocyanates and/or monoepoxide compounds.
Suitable OH components (I) of the two-component polyurethane adhesive are also polyether polyols, which are obtainable, for example, by adduction of ethylene oxide or propylene oxide with suitable polyols.
Suitable isocyanate group-containing components (II) of the polyureth~ne adhesive are, for example:
aromatic isocyanates, such as, for example, 2,4- and 2,6-tolylene diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene, 4,4-diphenyl, 1,5-naphthalene, 1,4-naph-thalene, 4,4-toluidine and xylylene diisocyanate, and substituted aromatic systems, such as, for example, dianisidine diiqocyanates, 4,4-diphenyl ether - `` ~ 9 9 2 diisocyanates or chlorodiphenylene diisocyanates, and higher-functional aromatic isocyanates, such as, for example, 1,3,5-triisocyanatobenzene, 4,4',4"-triiso-cyanattriphenylmethane [sic], 2,4,6-triisocyanato-toluene and 4,4'-diphenyldimethylmethane 2,2', 5,5'-tetraisocyanate; cycloaliphatic isocyanates, such as, for example, 1,3-cylocopentane [sic~ diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diiso~
cyanate and isophorone diisocyanate; aliphatic isocyanates, such as, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene and trimethylhexamethylene l,~-diisocyanate and tris(hexa-methylene) triisocyanate.
Furthermore, the isocyanate group-containing component (II) can also be a prepolymer of relatively high molecular weight. Compounds which may be mentioned here are adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethylene dii~ocyanate, and the trimers of hexamethylene diisocyante and of 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane.
.
The amount of component (II) is selected so that the ratio between the isocyanate groups of (II~
and the OH groups (I) is generally in the range from ~- 25 1:3 to 3:1. -~
Suitable isocyanate components (II) are, for :: , - -example, the isocyanate solutions commercially available under the name Desmodur0 N and Desmodur~ L
(Bayer AG). Suitable solvents for the isocyanate ~ . ~ ~ . ~ :, . - - : ~ . ,.: ~: ~ - . ::, , : , - ~136992 components are, for example, butyl acetate and ethyl acetate. A further suitable 2-component polyurethane adhesive is the adhesive obtainable under the trade name Adcote 549 B/Catalyst F from Morton International B.V.
The two-component adhesive used is particularly preferably an OH-containing polyester in which the carboxylic acid component is essentially or fully iæophthalic acid and/or terephthalic acid and the isocyanate component is a polyurethane prepolymer based on tolylene diisocyanate. The polyester may have been modified by means of diepoxide and/or monoepoxide compounds.
The production of the metal sheeting/poly-urethane adhesive layer/polypropylene copolymer plasticfilm composites i8 a process which i8 known in general terms. In this process, the two-component polyurethane adhesive BOlUtion i8 applied to the metal sheeting, and the polypropylene plastic film produced by extrusion is laminated onto the heated metal sheeting coated with the adhesive.
The coating of the metal sheeting or of the ,! ; film!adhesive composite produced generally has a total dry film thickness of less than 500 ~m, preferably from ;, :: : - - .: ~-10 to 200;~m and particularly preferably less than 100 ~m. The thickness of the adhesive layer is between 0.5 and 100 ~m. The thickness of the polypropylene film layer is correspondingly at values between 10 and 499.5 ~m.
-. - ....:.
-` 2~3~92 Finally, it should be pointed out that it is also possible to coat the metal sheeting on the side facing away from the contents with a preferably flat, thermoplastic composite film or alternatively with a liquid or pulverulent coating composition.
The composites according to the invention are employed for the production of packaging containers, in particular for the production of bases and lids of cans, valve disks or aerosol cans and of closure~. The closure parts are produced by conventional methods (cf.
for example, VR-INTERPACK 1969, pages 600-606 W. Panknin, A. Breuer, M. Sodeik, ~Abstreckziehen als Verfahren zum Herstellen von Dosen aus Wei~blech"
[Ironing as a Method for the Production of Cans from Tinplate], S~EET METAL INDUSTRIES, August 1976 W. Panknin, CH. Schneider, M. Sodeik, ~Plastic Deforma~
tion of tinplate in Can Manufacturing~; Verpackungs-Rundschau, i~sue 4/1971, pages 450-458- M. Sodeik, I. Siewert, "Die nahtlose Dose aus Wei~blech" [The Seamless Can Made from Tinplate]; Verpackungs-Rundschau, issue 11/1975, pages 1402-1407: M. Sodeik, K. Haa~, I. Siewert, "Herstellen von Dosen aus Wei~blech durch Tiefziehen" [Production of Cans from Tinplate by Deep Drawing], Arbeitsmappe fur den Verpackungspraktiker, Metalle, Part II, Group 2, Wei~blech [Tinplate], Serial No. 220.042 to 220.048 in neue Verpackung 12/87, page B 244 to B 246 and neue Verpackung 1/88, pages B 247 to B 250).
~ ~.
'~1369~2 For further details, reference is therefore made to the literature.
The polypropylene film/adhesive layer/metal sheeting composites according to the invention no longer have any significant stress whitening, and in addition the adhesion between the metal and the polyurethane adhesive on the one hand and the ~ polypropylene plastic film and/or polyurethane adhesive on the other hand is extremely good. The polypropylene outer layer protects the metal very well against attack by the contents, and effects on the contents by cor~
rosion products from the metal are likewise prevented.
Impairment of the contents by dissolved-out con-stituents of the polypropylene outer layer film is not observed during sterilization and storage of the packaged goods. In addition, the composites according to the invention can readily be produced since the bonding (lamination) of the polypropylene plastic film to the metal sheeting by means of the polyurethane adhesive at below the melting point of the polypropy-lene plastic can be carried out at the lamination rates which are usual in practice.
The invention is described below in greater ~ detail with reference to working examples~
-~ ~ 25 Example 1:
The polypropylene copolymer obtainable under the trade name Novolen 3225 MCX (BASF AG) is extruded by flat film die extrusion to give a 200 ~m thick plastic film. A two-component polyurethane adhesive -, ~.
,:
- 16 _ ~136~2 (Adcote 549 B/Catalyst F from Morton International B.V.) is knife-coated onto metal sheeting (12 g wet/m2), the adhesive-coated sheeting is placed in an oven (oven temperature 150C), and the pla~tic film is subsequently laminated at 100C onto the adhesive before the latter has cured completely. After 5 days, the adhesion is tested. It is greater than 20 N/25 mm.
After the composite has been stamped to give a can, no stress whitening is observed.
. - ~
~.,
PAT 92 354 FILE. ~ttN TH!S ~r1r`~ L L' ~;
7~ TRANSL~ N
22.04.1993 BASF Lacke + Farben Aktiengesellschaft, Munster Metal sheeting/polyurethane adhe~ive layer/poly-propylene copolymer pla~tic film co~posite, proce~s for its production, and its use for the production of packagi~g container~
. ' The present invention relates to a metal sheeting/ polyurethane adhesive layer/polypropylene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive. The present inventionfurthermore relatec to a process for the production of the composite and to the use of the composite for the production of packaging containers.
In the productio~ of a can or a closure for use as a packaging material, in particular for the packag-ing of foodstuff B ~ metal sheeting made from tinplate, ;-chromated steel, such as ECCS (electrolytic chromium-coated steel~ and aluminum in sheet or tape form are -coated. The lacquer film acts as a protective coating, ~-;~25 on the one hand for protecting the metal against attack by the contents and consequent corrosion and on the other hand for preventing the contents being affected by corrosion products from the metal. Naturally, the lacquer film it~elf, for example through di~solved-out lacquer constituents, must not affect or impair the ~ 2 contents, neither during the sterilization of the contents carried out after filling nor during subsequent storage of the packaged contents, in parti-cular food~tuffs.
Furthermore, the lacquers must be built up in such a way that they withstand the mechanical stresses which occur during further conversion of the coated sheeting to cans or closures, for example during shaping, stamping, flanging, creasing etc. of the sheeting.
In addition, the high solvent emissions during drying of the lacquer film mean that precautions must be taken to keep these emissions and the consequent environmental pollution as low as pos~ible.
An advantageous process for the coating of metal sheeting employed, in particular, for the production of foodstuff packaging has proved to be the coating of metal sheeting with films. Thus, DE-A 3 128 641, for example, describes a process for the production of laminates for foodstuff packaging in which the metal sheeting and a thermoplastic resin film together with an adhesive based on a carboxyl-containing polyolefin arranged between these layers is heated to temperatures above the melting point of the adhesive and then cooled together with application of precsure~ producing the metal/plastic composite.
Furthermore, DE-A 2 912 023, GB-A-2,027,391 and EP-B-31 701 disclose laminates and foodstuff packaging ~ 3~992 :~:
containers, in particular bags, produced from these laminates.
A multiplicity of composites of metal foils with polyolefin or polypropylene films is known.
Examples of adhesion promoter~ employed are polar-modified polypropylenes, eg. polypropylenes grafted with carboxylic acids or carboxylic anhydrides. Com-posites of this type are described, for example, in EP-A-101 250 and EP-A-312 306. It is furthermore known that metal sheeting/polypropylene plastic film compo-sites can be produced using solvent-containing two-component polyurethane adhesives. However, the problem occurs in polypropylene plastic film/metal sheeting composites that the plastic films bonded to the metal tend toward stress whitening. Otherwise, polypropylene plastic films have greater chemicals resistance than polyethylene plastic films.
The present invention thus had the object, in particular, of developing polypropylene plastic film/metal sheeting composites which do not exhibit stress whitening after shaping to form a packaging container. In addition, the adhesion of the plastic film to the metal sheeting should of course be excel-lent. Naturally, the thermoplastic polypropylene film should pro~ect the metal in an optimum manner against attack by the contents and consequent corrosion and prevent the contents being affected by corrosion products from the metal. Furthermore, the plastic film itself, for example through dissolved-out constituents, should of course not affect or impair the contents, neither during sterilization of the contents carried out after filling nor during subsequent storage of the packaged goods, in particular foodstuffs. In addition, it should be ensured that the bonding of the plastic film to the metal sheeting can be carried out at conventional lamination rates at temperatures above the melting point of the polypropylene plastic.
Surprisingly, this object is achieved by a metal sheeting/polyurethane adhesive layer/polypropyl-ene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive. The composite is characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copoly-merization of from 1 to 8% by weight of ethylene and/or further ~-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution MW:Mn in the range from 2 to 8 and a melt flow index MFI 230C/2.16 kg in the range from 5 to 10 g/10 min, preferably in the range from 6 to 10 g/10 min.
The invention also relates to a process for the production of the composite and to the use of the coated metal sheeting for the production of packaging containers.
'~3~9~ :
The advantages of the metal sheeting/two-component polyurethane adhesive layer/polypropylene copolymer plastic film composites according to the invention are, in particular, that the composites have no tendency toward stress whitening after shaping to form a packaging container.
Metal sheeting which is suitable for the pro-duction of the coated metal sheeting according to the invention is sheeting having a thickness of from 0.04 to 1 mm made from tin-free steel, tinplate, aluminum and various iron al oys, which may have been provided with a passivation coating based on compounds of nickel, chromium and zinc. Depending on the applica-tion, metal thicknesses of greater than 1 mm are also possible.
The metal sheeting is coated with thermoplastic polypropylene plastic film, the adhesion of the film to the metal sheeting being accomplished by means of a polyurethane adhesive.
The thermoplastic polypropylenes used to produce the plastic film are random polypropylene copolymers in the form of a film. These may also be composite films (multilayer films) obtained, for example, by joint extrusion of the polypropylene random copolymers.~ Polypropylene films of this type are pro-duced by known processes (blow processes, chill-roll processes, etc.) from granules of the polypropylenes.
The polypropylene copolymer plastic film of the composite according to the invention fully or ~136992 essentiall~ comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8%
by weight of ethylene and/or further ~-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition. Examples of further ~-monoolefins with the exception of propylene are, for example, C4-to C12- ~-monoolefins, such as 1-butene, 4-methyl-1-pentene, 1-hexene, 1-n-octene, 1-n-decene and 1-n-dodecene.
The polypropylene copolymer plastic film of the composite according to the invention is particularly preferably produced from a propylene copolymer obtained exclusively from the abovementioned amounts of ethylene and propylene.
The polypropylene copolymers have a molecular weight distribution MW:Mn in the range from 2 to 8 and a melt flow index MFI 230C/2.16 kg in the range from 5 to 13 g/10 min, preferably in the range from 6 to 20 10 g/10 min (measured in accordance with DIN 53 735).
The copolymer can be prepared by the polymeri-zation process described in DE-A 37 30 022 using a Ziegler-Natta catalyst system. For example, they are prepared by the so-called gas-phase polymerization 25 process at temperatures of from 20 to 160C and at a pressure of from 1 to 100 bar. The molecular weights of the polymers can be regulated by generally known measures, for example by means of hydrogen as poly-merization regulator or by peroxidic degradation.
._.. .. .
.~: ~. : .
213~992 The plastic films of the composites according to the invention are preferably obtained from poly-propylene copolymers prepared by random copolymeriza-tion of from 2 to 4% by weight of ethylene and from 98 to 96% by weight of propylene, based on the total weight of the monomer composition, the random copoly~
mers having a molecular weight distribution MW:Mn in the range from 2 to 5, particularly preferably in the range from 3 to 4, and a melt flow index MFI
230C/2.16 kg in the range from 5 to 10 g/10 min, particularly preferably in the range from 7 to 9 g/10 min (measured in accordance with DIN 53 735).
The polypropylene copolymers used in accordance with the present invention for the production of the metal/plastic film composites have a melting range of from about 135C to about 150C (determined by DSC).
They are obtainable, for example, under the trads name Novolen~ 3225 MCX (BASF AG).
The plastic of the plastic film used in the composite according to the invention preferably fully comprises the polypropylene copolymer described above.
However, it is also possible within the scope of the invention to extrude mixtures of the copolymer described and small amounts of other thermoplastics, preferably polypropylenes, to give a plastic film which can be employed in the composite. It is furthermore possible to employ multilayer films of said propylene copolymers which are obtainable by coextrusion.
~,. ~,.,_. .. - - - - - -3 5 9 ~ 2 ~ he thermoplastic polypropylene plastic film of the composite according to the invention may also contain conventional additives, such as, for example, internal and external lubricants, antiblocking agents, stabilizers, antioxidants, pigments, crystallization assistants and the like. These additives are employed in the amounts necessary for preparation, processing, make-up and use, in the form of powders, dusts, beads or a concentrate which is incorporated directly into the polymer. Further details on the amounts convention-ally employed and examples of suitable additive~ are given, for example, in Gachter-MUller, Kunststoff-additive, Carl-Hanser Verlag.
It is particularly advantageous if the thermo-plastic polypropylene films of the composites containup to 0.5% by weight, based on the total weight of the film, of erucamide and/or oleamide as lubricant and up to 0.2% by weight, based on the total weight of the plastic film, of antiblocking agent, preferably silicon dioxide, and if desired, antioxidants and, if desired, further processing stabilizers and further additives.
Preferred antioxidants are phenol derivatives.
Further suitable additives are titanium dioxide, calcium carbonate, diatomaceou~ earth, metal stearates and primary and secondary fatty acid amides. Examples of the W stabilizers employed are W stabilizers of the HALS type.
The adhesive layer arranged between the poly-propylene copolymer plastic film and the metal sheeting ~_.. ,, .. .. , . . , . . , . , -'~ 9 2 g may likewise contain the abovementioned additives.
However, these are preferably incorporated into the polypropylene plastic film.
The adhesive layer arranged between the metal sheeting and the polypropylene copolymer plastic film is obtained from a two-component, solvent-containing polyurethane adhesive. Any suitable proce~s can be used to apply the adhesive to the metal sheeting. The two-component polyurethane adhesive is applied by application from solutions in organic solvents. The solutions generally have an adhesive content of from 5 to 80% by weight. The amount of adhesive applied is generally from about 1 to 15 g/m2 [sic] of area.
The two-component polyurethane adhesive com-prises an OH-containing component (I), for example polyester-polyols, polyether-polyols or low-molecular-weight polyols, and an isocyanate group-containing component (II). The two components are mixed with one another immediately before application to the substrate.
Component (I) of the 2-component adhesive preferably comprises polye~ter-polyols. These are pre-pared by esterifying dicarboxylic acids by means of excess diols or polyols.
The esterification proceeds at elevated tem-perature in solution or in the melt. Dicarboxylic acids and glycols give linear polyesters, while esterifica-tion in the presence of triols and/or higher-functional polyols gives polyesters with a certain degree of ~13~992 branching. The polyester-polyols are obtainable by reacting polycar~oxylic acids or esterification-capable derivatives thereof, if desired together with mono-carboxylic acids, polyols, if desired together with monools, and, if desired, further modifying components.
Examples of suitable polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicar-boxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydro-phthalic acid, endomethylenetetrahydrophthalic acid, cyclohexanetetracarboxylic acid and cyclobutanetetra-carboxylic acid, Also suitable are the esterifiable derivatives of the abovementioned polycarboxylic acids, such as, for example, their monoesters or polyesters with aliphatic alcohols having 1 to 4 carbon atoms or hydroxy alcohols having 1 to 4 carbon atoms. In addition, the anhydrides of the abovementioned acids, if they exist, may also be employed.
If desired, monocarboxylic acids may also be employed together with the polycarboxylic acids;
examples are benzoic acid, tert-butylbenzoic acid, lauric acid, isononanoic acid and fatty acids of naturally occurring oils. The preferred monocarboxylic acid employed i~ isononanoic acid.
~1~6992 Suitable alcohol components for the preparation of the polyesters are polyhydric alcohols, such as ethylene glycol, propanediols, butanediols, hexanediols, neopentyl glycol, diethylene glycol, cyclohexanediol, cycloh~xanedimethanol, trimethyl-pentanediol, ethylbutylpropanediol, ditrimethylol-propane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, tris-hydoxyethyl [sic] isocyanurate, polyethylene glycol, polypropylene glycol, if desired together with monohydric alcohol~, such as, for example, butanol, octanol, lauryl alcohol, ethoxylated or propxylated [sic] phenols.
Suitable modifying components are polyiso-cyanates and/or diepoxide compounds, if desired alsomonoiQocyanates and/or monoepoxide compounds.
Suitable OH components (I) of the two-component polyurethane adhesive are also polyether polyols, which are obtainable, for example, by adduction of ethylene oxide or propylene oxide with suitable polyols.
Suitable isocyanate group-containing components (II) of the polyureth~ne adhesive are, for example:
aromatic isocyanates, such as, for example, 2,4- and 2,6-tolylene diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene, 4,4-diphenyl, 1,5-naphthalene, 1,4-naph-thalene, 4,4-toluidine and xylylene diisocyanate, and substituted aromatic systems, such as, for example, dianisidine diiqocyanates, 4,4-diphenyl ether - `` ~ 9 9 2 diisocyanates or chlorodiphenylene diisocyanates, and higher-functional aromatic isocyanates, such as, for example, 1,3,5-triisocyanatobenzene, 4,4',4"-triiso-cyanattriphenylmethane [sic], 2,4,6-triisocyanato-toluene and 4,4'-diphenyldimethylmethane 2,2', 5,5'-tetraisocyanate; cycloaliphatic isocyanates, such as, for example, 1,3-cylocopentane [sic~ diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diiso~
cyanate and isophorone diisocyanate; aliphatic isocyanates, such as, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene and trimethylhexamethylene l,~-diisocyanate and tris(hexa-methylene) triisocyanate.
Furthermore, the isocyanate group-containing component (II) can also be a prepolymer of relatively high molecular weight. Compounds which may be mentioned here are adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethylene dii~ocyanate, and the trimers of hexamethylene diisocyante and of 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane.
.
The amount of component (II) is selected so that the ratio between the isocyanate groups of (II~
and the OH groups (I) is generally in the range from ~- 25 1:3 to 3:1. -~
Suitable isocyanate components (II) are, for :: , - -example, the isocyanate solutions commercially available under the name Desmodur0 N and Desmodur~ L
(Bayer AG). Suitable solvents for the isocyanate ~ . ~ ~ . ~ :, . - - : ~ . ,.: ~: ~ - . ::, , : , - ~136992 components are, for example, butyl acetate and ethyl acetate. A further suitable 2-component polyurethane adhesive is the adhesive obtainable under the trade name Adcote 549 B/Catalyst F from Morton International B.V.
The two-component adhesive used is particularly preferably an OH-containing polyester in which the carboxylic acid component is essentially or fully iæophthalic acid and/or terephthalic acid and the isocyanate component is a polyurethane prepolymer based on tolylene diisocyanate. The polyester may have been modified by means of diepoxide and/or monoepoxide compounds.
The production of the metal sheeting/poly-urethane adhesive layer/polypropylene copolymer plasticfilm composites i8 a process which i8 known in general terms. In this process, the two-component polyurethane adhesive BOlUtion i8 applied to the metal sheeting, and the polypropylene plastic film produced by extrusion is laminated onto the heated metal sheeting coated with the adhesive.
The coating of the metal sheeting or of the ,! ; film!adhesive composite produced generally has a total dry film thickness of less than 500 ~m, preferably from ;, :: : - - .: ~-10 to 200;~m and particularly preferably less than 100 ~m. The thickness of the adhesive layer is between 0.5 and 100 ~m. The thickness of the polypropylene film layer is correspondingly at values between 10 and 499.5 ~m.
-. - ....:.
-` 2~3~92 Finally, it should be pointed out that it is also possible to coat the metal sheeting on the side facing away from the contents with a preferably flat, thermoplastic composite film or alternatively with a liquid or pulverulent coating composition.
The composites according to the invention are employed for the production of packaging containers, in particular for the production of bases and lids of cans, valve disks or aerosol cans and of closure~. The closure parts are produced by conventional methods (cf.
for example, VR-INTERPACK 1969, pages 600-606 W. Panknin, A. Breuer, M. Sodeik, ~Abstreckziehen als Verfahren zum Herstellen von Dosen aus Wei~blech"
[Ironing as a Method for the Production of Cans from Tinplate], S~EET METAL INDUSTRIES, August 1976 W. Panknin, CH. Schneider, M. Sodeik, ~Plastic Deforma~
tion of tinplate in Can Manufacturing~; Verpackungs-Rundschau, i~sue 4/1971, pages 450-458- M. Sodeik, I. Siewert, "Die nahtlose Dose aus Wei~blech" [The Seamless Can Made from Tinplate]; Verpackungs-Rundschau, issue 11/1975, pages 1402-1407: M. Sodeik, K. Haa~, I. Siewert, "Herstellen von Dosen aus Wei~blech durch Tiefziehen" [Production of Cans from Tinplate by Deep Drawing], Arbeitsmappe fur den Verpackungspraktiker, Metalle, Part II, Group 2, Wei~blech [Tinplate], Serial No. 220.042 to 220.048 in neue Verpackung 12/87, page B 244 to B 246 and neue Verpackung 1/88, pages B 247 to B 250).
~ ~.
'~1369~2 For further details, reference is therefore made to the literature.
The polypropylene film/adhesive layer/metal sheeting composites according to the invention no longer have any significant stress whitening, and in addition the adhesion between the metal and the polyurethane adhesive on the one hand and the ~ polypropylene plastic film and/or polyurethane adhesive on the other hand is extremely good. The polypropylene outer layer protects the metal very well against attack by the contents, and effects on the contents by cor~
rosion products from the metal are likewise prevented.
Impairment of the contents by dissolved-out con-stituents of the polypropylene outer layer film is not observed during sterilization and storage of the packaged goods. In addition, the composites according to the invention can readily be produced since the bonding (lamination) of the polypropylene plastic film to the metal sheeting by means of the polyurethane adhesive at below the melting point of the polypropy-lene plastic can be carried out at the lamination rates which are usual in practice.
The invention is described below in greater ~ detail with reference to working examples~
-~ ~ 25 Example 1:
The polypropylene copolymer obtainable under the trade name Novolen 3225 MCX (BASF AG) is extruded by flat film die extrusion to give a 200 ~m thick plastic film. A two-component polyurethane adhesive -, ~.
,:
- 16 _ ~136~2 (Adcote 549 B/Catalyst F from Morton International B.V.) is knife-coated onto metal sheeting (12 g wet/m2), the adhesive-coated sheeting is placed in an oven (oven temperature 150C), and the pla~tic film is subsequently laminated at 100C onto the adhesive before the latter has cured completely. After 5 days, the adhesion is tested. It is greater than 20 N/25 mm.
After the composite has been stamped to give a can, no stress whitening is observed.
. - ~
~.,
Claims (7)
1. Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive, characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8% by weight of ethylene and/or further .alpha.-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution Mw:Mn in the range from 2 to 8 and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min, preferably in the range from 6 to 10 g/10 min.
polypropylene copolymer plastic film composite in which the adhesive layer is obtained from a solvent-containing two-component polyurethane adhesive, characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer obtainable by random copolymerization of from 1 to 8% by weight of ethylene and/or further .alpha.-monoolefins, with the exception of propylene, and from 99 to 92% by weight of propylene, based on the total weight of the monomer composition, the polypropylene copolymer having a molecular weight distribution Mw:Mn in the range from 2 to 8 and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min, preferably in the range from 6 to 10 g/10 min.
2. Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite accord-ing to claim 1, characterized in that the random polypropylene copolymer is obtained exclusively by random copolymerization of ethylene and propylene.
polypropylene copolymer plastic film composite accord-ing to claim 1, characterized in that the random polypropylene copolymer is obtained exclusively by random copolymerization of ethylene and propylene.
3. Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite accord-ing to claim 1 or 2, characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer comprising from 2 to 4% by weight of ethylene and from 98 to 96% by weight of propylene, based on the total weight of the monomer composition, having a molecular weight distribution Mw:Mn in the range from 2 to 5, particularly preferably in the range from 3 to 4, and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min, particularly preferably in the range from 7 to 9 g/10 min.
polypropylene copolymer plastic film composite accord-ing to claim 1 or 2, characterized in that the polypropylene copolymer plastic film essentially or fully comprises random polypropylene copolymer comprising from 2 to 4% by weight of ethylene and from 98 to 96% by weight of propylene, based on the total weight of the monomer composition, having a molecular weight distribution Mw:Mn in the range from 2 to 5, particularly preferably in the range from 3 to 4, and a melt flow index MFI 230°C/2.16 kg in the range from 5 to 10 g/10 min, particularly preferably in the range from 7 to 9 g/10 min.
4. Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite accord-ing to claim 1 to 3, characterized in that the polypropylene plastic film contains up to 0.5% by weight, based on the total weight of the plastic film, of erucamide and/or oleamide and up to 0.2% by weight, based on the total weight of the plastic film, of antiblocking agent, preferably SiO2 [sic], and if desired, antioxidants and, if desired, further processing stabilizers and further additives.
polypropylene copolymer plastic film composite accord-ing to claim 1 to 3, characterized in that the polypropylene plastic film contains up to 0.5% by weight, based on the total weight of the plastic film, of erucamide and/or oleamide and up to 0.2% by weight, based on the total weight of the plastic film, of antiblocking agent, preferably SiO2 [sic], and if desired, antioxidants and, if desired, further processing stabilizers and further additives.
5. Metal sheeting/polyurethane adhesive layer/
polypropylene copolymer plastic film composite accord-ing to claim 1 to 4, characterized in that the two-component polyurethane adhesive used is a hydroxyl group-containing polyester in which the carboxylic acid component is essentially or fully isophthalic acid and/or terephthalic acid, and an isocyanate group-containing polyurethane prepolymer composition based on tolylene diisocyanate.
polypropylene copolymer plastic film composite accord-ing to claim 1 to 4, characterized in that the two-component polyurethane adhesive used is a hydroxyl group-containing polyester in which the carboxylic acid component is essentially or fully isophthalic acid and/or terephthalic acid, and an isocyanate group-containing polyurethane prepolymer composition based on tolylene diisocyanate.
6. Process for the production of the metal sheeting/polyurethane adhesive layer/polypropylene copolymer plastic film composite according to claim 1 to 5, characterized in that the two-component polyurethane adhesive is applied to the metal sheeting, and the polypropylene plastic film is laminated onto the heated, adhesive-coated metal sheeting,
7. Use of the metal sheeting/polyurethane adhesive layer/polypropylene copolymer plastic film composites according to claim 1 to 5, for the production of packaging containers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4217935.1 | 1992-05-30 | ||
| DE4217935A DE4217935A1 (en) | 1992-05-30 | 1992-05-30 | Metal sheet - polyurethane adhesive layer - polypropylene copolymer - plastic film composite, process for its production and its use for the production of packaging containers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136992A1 true CA2136992A1 (en) | 1993-12-09 |
Family
ID=6460084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136992A Abandoned CA2136992A1 (en) | 1992-05-30 | 1993-05-25 | Metal sheeting/polyurethane adhesive layer/polypropylene copolymer plastic film composite, process for its production, and its use for the production of packaging containers |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0642415B1 (en) |
| JP (1) | JPH08501029A (en) |
| AT (1) | ATE135629T1 (en) |
| AU (1) | AU670095B2 (en) |
| CA (1) | CA2136992A1 (en) |
| DE (2) | DE4217935A1 (en) |
| NO (1) | NO944568L (en) |
| WO (1) | WO1993024319A1 (en) |
| ZA (1) | ZA933549B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4218369A1 (en) * | 1992-06-04 | 1993-12-09 | Basf Lacke & Farben | Process for the production of a metal-plastic film composite, metal-plastic film composite produced by this process and its use for the production of packaging containers |
| DE4229419A1 (en) * | 1992-09-03 | 1994-03-10 | Basf Lacke & Farben | Polypropylene film - adhesion promoter - metal composite and its use for the production of packaging containers |
| DE19534011A1 (en) * | 1995-09-14 | 1997-03-20 | Basf Lacke & Farben | Direct extrusion composites |
| DE20005621U1 (en) * | 1999-03-25 | 2000-08-24 | Hewing Gmbh | Metal-plastic composite pipe |
| AT518457B1 (en) * | 2016-04-04 | 2018-03-15 | Constantia Teich Gmbh | Packaging laminate with a carrier layer and a polyolefin layer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE790028A (en) * | 1971-10-19 | 1973-04-13 | Aluminum Co Of America | METHOD OF MANUFACTURING A LAMINATED METAL WALL OF A CONTAINER PROVIDED WITH AN OPENING DEVICE, AND LAMINATED METAL WALL OF A CONTAINER MANUFACTURED BY THIS PROCESS |
| EP0022502A1 (en) * | 1979-07-04 | 1981-01-21 | Herberts Gesellschaft mit beschränkter Haftung | Laminate, method of its manufacture and use of silanes therefor |
| CA1243257A (en) * | 1983-10-18 | 1988-10-18 | Masakazu Ito | Multi-layer film or sheet material |
| DE3436820A1 (en) * | 1984-10-06 | 1986-04-17 | Basf Ag, 6700 Ludwigshafen | COMPOSITE |
| US4839234A (en) * | 1986-05-13 | 1989-06-13 | Sumitomo Chemical Company, Limited | Polypropylene film |
| JPH0699677B2 (en) * | 1990-01-08 | 1994-12-07 | サンスター技研株式会社 | Polyurethane adhesive |
-
1992
- 1992-05-30 DE DE4217935A patent/DE4217935A1/en not_active Withdrawn
-
1993
- 1993-05-21 ZA ZA933549A patent/ZA933549B/en unknown
- 1993-05-25 WO PCT/EP1993/001305 patent/WO1993024319A1/en active IP Right Grant
- 1993-05-25 JP JP6500179A patent/JPH08501029A/en active Pending
- 1993-05-25 CA CA002136992A patent/CA2136992A1/en not_active Abandoned
- 1993-05-25 DE DE59301979T patent/DE59301979D1/en not_active Expired - Fee Related
- 1993-05-25 AT AT93912779T patent/ATE135629T1/en not_active IP Right Cessation
- 1993-05-25 AU AU43171/93A patent/AU670095B2/en not_active Expired - Fee Related
- 1993-05-25 EP EP93912779A patent/EP0642415B1/en not_active Expired - Lifetime
-
1994
- 1994-11-29 NO NO944568A patent/NO944568L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0642415B1 (en) | 1996-03-20 |
| AU4317193A (en) | 1993-12-30 |
| ZA933549B (en) | 1993-12-10 |
| EP0642415A1 (en) | 1995-03-15 |
| AU670095B2 (en) | 1996-07-04 |
| WO1993024319A1 (en) | 1993-12-09 |
| DE4217935A1 (en) | 1993-12-02 |
| NO944568D0 (en) | 1994-11-29 |
| NO944568L (en) | 1994-11-29 |
| DE59301979D1 (en) | 1996-04-25 |
| ATE135629T1 (en) | 1996-04-15 |
| JPH08501029A (en) | 1996-02-06 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |