CA2118912C - Peelable laminated structures and process for production thereof - Google Patents

Abstract

The invention provides a peelable laminated structure suitable for use in a peelable seal joining a flexible closure element (23) to a container (20) or in foil/polymer laminates used for packaging and the like. The structure comprises a porous-anodiz-able metal substrate (11) and a porous anodic film (12) overlying and attached to a surface of the substrate. The porous anodic film (12) has a weakened stratum (19) positioned between an outer film part and an underlying structure including the metal substrate (11). The weakened stratrum (19) is strong enough in use of said structure to prevent detachment of the outer film part from the underlying structure, except by deliberate peeling of the flexible closure element (23). The invention also relates to a process for producing the structure and to peelable containers and recyclable laminates incorporating the structure. The structure provides a peelable interface which is not greatly dependent on the characteristics of particular adhesives or bonding techniques used to adhere the metal substrate (11) to the remaining structure, and is thus stable and reliable.

Description

....~

PEELABLE LAMINATED STRUCTURES AND PROCESS FOR PRODUCTION
THEREOF

TECHNICAL FIELD
This invention relates to peelable structures which can be used for joining metal layers to layers of other - materials in such a way that separation of the layers does not take place during normal handling of the resulting articles, but separation can be brought about by peeling, when desired. The invention also relates to a process for 10 producing such structures and articles containing the structures.
BACKGROUND ART
Peelable laminated structures are used, in particular, in container and packaging technologies.
15The use of containers made of metal, metal foil, plastic or glass and provided with peelable closure elements, such as covers, seals, lids or other sealing elements made of metal foil or flexible plastics, is widespread nowadays. For example, containers of this kind ~
20 are used for packaging hllr~n and animal foodstuffs and for -protecting articles which have to be kept sanitary or sterile, e.g. medical instruments or equipment, pharmaceutical doses, and the like. The advantage of using containers of this type is that the they are 25 generally inexpensive, can be sealed hermetically and can be opened easily by hand or simple machine.
Sealed containers of this kind may be produced in a variety of types, shapes and sizes. For example, the containers may consist of rigid or semi-rigid shape~
30 hollow bodies having thin flexible metal or plastic lids or may be in the form of flexible metal or plastic pouches having seams which can be peeled apart. The use of metal foils to form part or all of such containers is common because metal foils have good oxygen and moisture barrier 35 properties, good mechanical and thermal properties and can be made to look attractive.

211~12 -"

Peelable sealed packages are conventionally made by attaching a closure element to a container by means of an adhesive, a heat sealable lacquer or a heat sealable polymer membrane (usually a polypropylene membrane) having a sufficient adhesive strength to prevent the container from opening prematurely, but nevertheless having a strength low enough to permit the closure element to be peeled away from the container by hand or simple machine when the-container is to be opened. Incidentally, to avoid unnecessary repetition, adhesives, lacquers and polymer membranes are referred to collectively throughout the following description and claims merely as "adhesives."
While many peelable adhesives are already known, not all are suitable for use in all cases. For example, the choice of a suitable adhesive is particularly difficult when the container is to be heated prior to being opened, --for example if it contains a foodstuff to be served hot or if it contains an item to be pasteurized (heated for a short period at about 80 - 85 C) or sterilized (heated for a longer time usually at a temperature in the range of 120 - 130-C) in heated water or other heating medium. In such circumstAnc~s, the adhesive strength is often changed (usually substantially reduced, often by a factor of two or more) during the heating step, l~ing to a premature failure of the seal or to difficulty when opening the container. To make matters worse, the extent of-the change in the adhesive strength is often difficult to predict as it can be very sensitive to variations in adhesive formulations and to variations of time and temperature of the heating process. The presence of moisture or steam can also have a significant effect on the adhesive strength.
Even when the container is not to be subjected to a 35 heating step prior to use, the adhesive still has to be carefully chosen in order to provide a peel strength sufficient to provide an effective and durable seal, while W093/06992 ~118 9 12 PCT/CA92/00433 . .

at the same time allowing the container to be opened easily. In the case of products having a long shelf life, the choice of suitable adhesives may be further limited by the need to avoid adhesives which change adhesive 5 properties with age, and in the case of containers intended to hold foodstuffs or other comestibles, the choice is limited to adhesives approved by health care regulations.
In consequence, it will be appreciated that a certain 10 amount of care is required in the choice and application of adhesives for peelable containers, and this often translates into more expensive products or to a limitation of the use of peelable sealed contAiners for certain items or applications.
It would therefore be advantageous to provide ~;
peelable sealed containers incorporating peelable structures having peel characteristics which are less dependent on the choice of the sealing adhesives and which are less sensitive to variations in temperature and 20 processing times.
~ urthermore, there is a need for peelable structures of this kind which may be used for applications other than in peelable containers. For example, flexible packaging films often consist of one or more polymer layers laminated to a metal foil so that a desired combination of properties of both materials can be obtained. However, laminated materials of this kind are difficult or expensive to recycle and recyclability is becoming increasingly important both at the factory level (to deal 30 with internally generated scrap, trimmings, etc.) and at the consumer level after sale and use. The difficulty is caused by the bonding together of two different types of materials (metal and plastics) which are recycled by different methods. It would therefore be advantageous to 35 produce laminated films of this kind which could be easily ; separated into their component materials when desired simply by peeling the materials apart by hand in order to ... . .. . .. . . . ... ..

facilitate recycling.
OBJECTS OF THE INVENTION
An object of the invention is therefore to provide a peelable laminated structure suitable for the above-5 mentioned uses and which overcomes some or all of theabove-mentioned drawbacks.
Another object of the invention is to provide such a structure having a peel strength which is affected to a lesser extent by adhesives or other means used to attach the structure to a contAiner~ closure element or polymer layer.
Another object of the invention is to provide a peelable structure which shows reduced variation of peel strength upon exposure of the s~ructure to high temperatures, e.g. such as those which are commonly used for preparing foods or sterilizing equipment, or to aging.
Another object of the invention is to provide a process for producing such structures which can be operated economically and with consistent results.
DISCLOSURE OF THE I~v~ ON
According to one aspect of the present invention there is provided a peelable structure suitable for attaching a metal layer to other layers of a laminated article, the structure comprising a substrate comprising a ~5 porous-anodizable metal at its surface, and a porous anodic film overlying and attached to the surface. The porous anodic film is provided with a weakened stratum positioned between an outer film part and an underlying part including the substrate, the weakened stratum being strong enough in use of the structure to prevent detachment of the outer film part from the underlying part, except by deliberate peeling apart of the metal layer and the other layer of the laminated article.
According to another aspect of the invention, there is provided a process for producing a peelable structure suitable for attaching a metal layer to other layers of a laminated article. The process comprises anodizing a W093/06992 ~ 21 1 8 9 1 2 PCT/CA92~00433 surface of a porous anodizable metal in an electrolyte at a voltage which results in the formation of a porous anodic film, continuing the porous anodization while carrying out a voltage reduction procedure in order to introduce a weakened stratum into the anodic film, and allowing the film to stand in said electrolyte or other acidic solution for a period of time ~o further weaken the film along the stratum; wherein the voltage and the period of time are made such that, under the conditions employed, 10 the weakened stratum is strong enough in use of the structure to prevent detachment of the outer film part from the underlying structure, except by peeling apart of the metal layer and the other layers of the laminated article.
15The invention also relates to peelable closed containers, such as rigid or semi-rigid cont~inPrs or flexible packages or po~lr~eC, incorporating the peelable structures of the present invention, and peelable lidding materials, cont~inPr bodies and packaging films incorporating the peelable structures.
The peelable structures of the present invention not only make the selection of adbesive or lacquer used to form a peelable seal less important, but have peel strengths that are largely unaffected by heat or aging.
25 Moreover, since the structures incorporate porous anodized films, which are ideal for bonding to adhesives or lacquers, the need for pre-treatments-of metal foils used for containers to make them more receptive to adhesives has been largely eliminated. Since such pre-treatments 3Q often required the use of chromates, which are difficult and expensive to dispose of, this is a considerable advantage. The structures also make it possible to separate foil/polymer laminates when desired, e.g. for - recycling.

Figs. l(A) to l(D) are schematic cross-sections showing steps in a preferred process according to the w093/06992 PCT/CA92/0~33 pxesent invention;
Fig. 2 is an enlarged partial cross-section of a container provided with a lid made of a lidding material according to one embodiment of the invention;
Fig. 3 is a partial cross-section similar to that of ;
Fig. 2 showing a lidding material according to a second embodiment of the invention;
Fig. 4 is a partial cross-section showing a further embodiment of the present invention:
Fiq. 5 is a cross-section of a laminated packaging film according to a further ~hoAiment of the present -~
invention; and Fig. 6 is a cross-section of an apparatus for operating a process of the invention on a continuous basis.
BEST MODES FOR CARRYING OUT THE lNv~ ON -~
In the present invention, use is made of the discovery that it is possible to form an anodic metal oxide film provided with a weakened internal stratum on the surface of an anodizable metal substrate and to use the w~ened stratum to enable the anodic film, and any material attached to the film, to be detached from the metal substrate, when desired. In this way, if a material is attached to the oxide film by means of an adhesive or 25 by direct bonding, the force required for detachment of the material from the metal substrate is not greatly ' dependent on the adhesive or bonding strength, but rather upon the internal strength of the anodic film at the level of the weakened stratum. Consequently, provided the strength of the adhesive is and remains greater than the strength of the oxide film at the weakened stratum, the peel strength of the laminated structure is not greatly influenced by the way in which the various layers are bonded together. Because the peel strength of the oxide film is substantially unaffected by heat and aging, the resulting laminated structure is more stable over time than many similar structures which depend on peeling of an adhesive layer or the like. Moreover, when an adhesive is employed, less attention has to be paid to the nature of ~-the adhesive and less expensive adhesives can often be used although, of course, adhesives suitable for use with -foodstuffs must be selected in those cases where the structure is to be used in containers for foodstuffs, and adhesives capable of withstanding heat must be selected in those c~cPs where the structure is to be used in retortable containers. Despite these considerations, adhesives may be selected from a large group, depending on the application. For example, Morprime lOB (trade-mark of Morton International), a heat seal lacquer that is -commonly used for retortable containers, is suitable in the present invention for many applications.
Having said that the peel strength is not greatly affected by the choice of adhesive, it should be pointed out that the peel strength is not always completely unaffected by the chosen adhesive. This is because the adhesive, or certain components of the adhesive, may 20 penetrate into the pores in the anodic film to the level of the weakened stratum and exert an influence on the peeling operation. Different adhesives moderate the expected peel strength by different amounts and thus the choice of adhesive can be used to "fine tune" the peel strength, if desired.
The process of the present invention begins with the formation of a porous anodic film on a metal substrate and involves the formation of a weakened stratum within the film. The presence of the weakened stratum is necessary 30 because anodic films normally adhere tenaciously to the metal sub$trates on which they are formed by electrolysis and cannot usually be peeled away from the metal by any means.
The formation of a weakened stratum in a porous anodic film has been described in our prior European Patent Publication No. EP 0 128 831 filed in the name of Robin Christopher Furneaux. The various steps in the W093/06992 - PCT/CA92/~33 21189i2` 8 method, with modifications suitable for the present invention, are shown in simplified form in Figs. l(A) to l(D) of the accompanying drawings. Fig. l(A) shows a ;
metal substrate 11 made, for example, of aluminum or an anodizable aluminum alloy, on the outer surface 13 of which the weakened anodic film is to be formed. This substrate is subjected to anodization in an electrolyte containing an acid, such as phosphoric acid or sulphuric acid, which results in the formation of a porous anodic film 12 as shown in Fig. l(B) on the surface 13 of the substrate. The film 12 has numerous pores 14 which are open ended at the outer surface 15 of the film and which extend inwardly towards the metal substrate 11. The pores 14 do not extend completely to the substrate 11 and remain separated from the substrate by a thin, dense non-porous barrier layer 16 of ~noAiC oxide. This barrier layer adheres tenaciously to the metal 11 and prevents easy removal of the film 12 from the substrate.
The pores 14 are formed as a result of a competition 20 between oxide formation resulting from the anodization and oxide dissolution by the acidic electrolyte. The oxide film increases in thickness as the electrolysis proceeds but eventually a maximum thickness is achieved at which overall oxide formation and oxide dissolution are about the same.
Fig. l(C) shows the result of a step carried out after the initial anodization resulting in the formation of the porous layer of Fig. l(B). This additional step involves continued anodization in the same or a similar electrolyte while carrying out a voltage reduction procedure. As the voltage is re~uceA, the field across the barrier layer 1~ is reduced and the current initially stops flowing. With time, the oxide in the pore walls and barrier layer begins to dissolve and the dissolution is fastest in the barrier layer. Eventually, the barrier layer is reduced in thickness to a point where the anodizing current can begin to flow once more at the W093/06~2 211 S 9 ~ 2 PCT/CA92/~33 g :~
reduced voltage. A new layer of porous oxide is then ~;
formed, but the new growth has a smaller pore size and pore wall thickness than the original film and there is an increase in the number of pores as a result of pore 5 branching. Repeated voltage reduction of this kind, which - may be carried out in steps or continuously, results in a progressive refinement of the pores resulting in the formation of branched pore regions 17 at the bottoms 18 of ;~
the pores 14 formed in the original film. A final period of soaking of the film in the electrolyte or other solution containing an oxide-etching acid, thins the pore walls further. In the region of the film formed prior to the pore-br~nc~ing step, this has only a small effect on the pore size and film strength. In the branched pore region 17, however, significant weAkening of the film is produced because of the smaller pore wall thi~n~sc. As a result, the branched pore regions 17 collectively form a we~k~n~ stratum lg in the film in which the barrier layer is extremely thin or non-existent. This makes it possible 20 to detach the film 12 from the substrate 11 along the weakened stratum.
Although the anodization process is normally terminated at the point shown in Fig. l(C), it is possible to carry out further normal porous anodization after the 25 voltage reduction and soaking steps in order to grow further porous anodic film 12 beneath the weakened stratum 19 as shown in Fig. l(D). In this way, the weakened stratum 19 can be positioned at virtually any level within the anodic film 12, as desired.
Although this basic procedure is shown in our European Patent publication referred to above, the anodization in the prior publication is commenced at a relatively high voltage (typically greater than 100 V) and is continued until a relatively thick (about 50x104 cm r50 35 microns]) film is formed. The voltage reduction p~oued~re is carried out over a period of 30 minutes or so until the anodic film completely detaches itself from the underlying W093/069g2 PCT/CA92/00433 211~!312 : ~

metal. In the present invention, it is essential that the anodic film remain attached to the underlying metal.
Moreover, the relatively thick anodic films produced according to the prior publication are incompatible with flexible packaging handling machinery. Thus, for example, passing the thick anodized foil over rolls would cause severe crazing and possible spalling of the oxide and this could lead to problems of seal integrity, etc. Moreover, the processing times employed make the process unacceptable for commercial operations in the field of technology to which the present invention primarily relates, i.e. the container and packaging arts.
Accordingly, some modification of the disclosed process is required.
The inventors of the present invention have studied this problem and have identified factors which can affect the peel strength of the resulting film and whi~h can make the process more economical and applicable to ~hi n"~r, flexible anodic films. In particular, it has now been found that the final peel strength of the anodic film can be controlled by the following factors.

1. Acid type and concentration.
Since oxide dissolution rates are different for the various commonly used anodizing acids, the oxide films produced by using different acids are differ~nt and have different weakening characteristics. For example, phosphoric acid dissolves anodic aluminum oxide faster than sulfuric acid (at equivalent concentrations and temperatures). This means that, using phosphoric acid, the voltage reduction procedure can be carried out relatively quickly, and the final eo~ki ng time can be short. With sulfuric acid, the voltage reduction stage takes longer, and a much longer final soak is required.
For many applications, a lM roncentration of phosphoric acid is suitable. For more dilute acid solutions, the processing time is extended and this W093/06~2 211~ 9 12 PCT/CA92/00433 reduces linespeeds in continuous operations and increases costs. For more concentrated acid solutions, the processing time is reduced, but this can make control of the peel strength more difficult (since very short soak times may need to be accurately controlled). For phosphoric acid, concentrations in the range of 0.1 to 2.0 M are usually suitable.
It will therefore be seen that, for rapid continuous processes, phosphoric acid is preferred. It should also 10 be noted that phosphoric acid is more compatible for use with food tha~ some other possible acids (e.g. chromic acid, oxalic acid and sulfuric acid), and thus more desirable when the product is to be used in these applications.

2. Operating temperature.
Since oxide dissolution rates and electrical conductivities are temperature dependent, the oxide film structure and its weakening behaviour can be influenced by the operating temperature. Higher temperatures reduce the 20 time required for the voltage reduction and final soak stages.
In continuous processes, the anodizing current generates some heat and therefore it is advantageous to operate the process at temperatures above ambient (to avoid the need for an auxiliary cooling system). For such a process, tem~eratures of between about 50-C and 60-C are preferred, particularly when using lM phosphoric acid as the electrolyte.

3. Initial anodizing voltage and voltage reduction 30 procedure.
Selection of an appropriate initial anodizing voltage is important for two reasons. Firstly, the initial Ano~1zing voltage controls the structure of the ~Yro~
surfacé of the anodic film to which the adhesive must bond. Secondly, this voltage also fixes the starti~g .

W093~06992 ~ PCT/CA92/00433 21189i2 --point for the ~oltage reduction procedure. It has been found that a preferred range for the starting voltage is between about 5 volts and about 20 volts. Over this range, the surface of the anodic oxide bonds well to heat S seal lacquers and other adhesives. By using these relatively low anodizing voltages, the voltage reduction stage is correspondingly short.
The voltage reduction stage involves a stepwise or continuous decrease in the applied voltage. After each 10 voltage reduction step, the anodizing current initially falls, and after a short period (during which the barrier oxide is dissolving) it begins to recover to a new, slightly lower current. The time between voltage reductions can be adjusted to allow full current recovery.
15 However, surprisingly, it has now been found that it is not necessary to achieve full current recovery at each stage. By choosing voltage reduction steps and times which allow partial current recovery to occur at each stage, only part of the surface area of the sample is 20 undergoing anodization. This gives an additional method for controlling the strength of the weakened stratum.
Furthermore, the incomplete current recovery procedure reduces the time required for the voltage reduction stage.
The final voltage (at the end of the voltage reduction sequence) determines the pore structure of the anodic film at the interface. In order to ~; ni~i se the final soak time, this voltage should be small (e.g.
preferably 1 volt or less).

4. Final soak time.
The final soak stage is designed to partially dissolve the pore walls of the anodic film, so that in regions where the finest pore structure occurs, the strength of the oxide is reduced to a desirable value.
For a given film structure, the peel strength of the anodic film is higher for shorter soak tîmes.
For continuous processing, short soak times W093/06992 ~ 1 1 8 9 1 2 PCT/CA92/00433 (preferably a few seconds) are desired. However, when the soak times for a given peel strength are too short, it may :
be difficult to control the peel strength and may lead to variable properties.
While the focus of the present invention is preferably on the achievement of rapid low cost production processes for commercial reasons, it will be clear that the factors outlined above can be used to achieve a wide range of anodic film structures with a range of peel strengths. Thus peel strengths can be tailored to meet the requirements of particular applications.
As will be apparent from the factors discussed above, a preferred process for producing a structure capable of being peeled manually involves low starting voltages (e.g.

5-15 volts), short anodization periods (e.g~ less than one minute and preferably 10-30 seconds), high electrolyte temperatures (e.g. 40-60-C) and high acid concentrations (e.g. lM H3P04). The voltage reduction procedure preferably employs a stepwise or continuous reduction of 20 voltage of between about 0.2 and 2 volts~second and a ~
final soaking period at a voltage of less than or equal to -lV for as little as 2 seconds. The short anodization times and low voltages mean that the resulting anodic films are quite thin, i.e. up to about 25x104 cm t25 25 microns], but usually less than lx104 cm, [1 micron] and optionally îess than O.lxlO 4 cm [0.1 micron~, but they are nevertheless capable of contA;ning the required w~Aken~
stratum. In practice, economics and performance constraints govern the oxide thickness. These conditions 30 make the above process commercially attractive and capable of being carried out, if desired, on a continuous basis, but alternative conditions, e.g. higher starting voltages, may be employed, if desired.
The peel strength along the weAk~ned stratum in the structures of the present invention should be such that detachment does not occur accidentally during normal use of the products containing the structures, but such that W093/06992 PCT/CA92/~33 211891~

detach~nt can be brought about by deliberate peeling.
The force required to peel the structure varies from application to application, and depends to some extent on the nature of the product con~aining the weakened stratum, e.g. the area of attachment of the various layers in the laminate. Relative peel strengths can be compared more accurately by making various samples of the same width and peeling constituent layers of the structures apart from each other at an angle of 180-. Using this comparison, 10 the structures of the present invention can be manufactured in such a way as to produce a wide range of peel strengths, although for the applications men~ioned, these would typically fall within the range: o.3 N/cm to 10 N/cm. For special applications, higher peel strengths can be achieved. As an example, for a peelable foil lidding material used on ALUCONT~ 350120F containers, (manufactured by Alcan Deutschland GmbH, Ohle Works), peel strengths, as defined above, are preferably in the range between about 1.5 N/cm to 5 N/cm. In practice, this corresponds to a peel force (at a constant 90- angle of peel) of 8-12 N.
As mentioned briefly earlier, peel strengths may be affected to some extent by the adhesives used to attach the anodic film to an adjacent element ~uch as a peelable lid. It should be kept in mind that the anodic films utilized in the invention are usually very thin, so the weakened stratum is never very-far from the outer surface of the film and thus never far from the adhesive layer.
Penetration of the adhesive into the weakened stratum is 30 therefore quite possible. Since the position of the weakened stratum within the thickness of the anodic film can itself be controlled by the pro~edu~e expl~;~e~ in connection with Fig. l(D) and since penetration is more likely when the weakened stratum is closer to the surface, 35 penetration by the adhesive can be made more or less likely; as desired, for any particular film thickness.
This is a further means of controlling the effect of the W093/06992 2 ~ 18 91 ~ PCT/CA92/~433 . .

adhesive on the peel strength in addition to the choice of adhesive itself.
In general, it has been found that when using a thermoplastic heat-seal lacquer (e.g. Morprime loB), a small increase in peel strength is observed after retorting samples for 30 minutes at 130C. This is attributed to migration of polypropylene from the lacquer into the pores such that the weakened stratum is slightly reinforced. A typical peel force increase produced in this way is from about lON to llN. This compares favourably with the dramatic change in peel strength observed in some conventional "lacquer controlled" peel systems where peel forces may decrease from more than about 2ON down to about llN.
Thus, the weakened stratum in the oxide layer is the main factor controlling peel strength when th~ heat seal lacquer is of the thermoplastic type. However, the --lacquer can make a small contribution to the peel strength under some circumstances (e.g. after elevated temperature/
20 time treatment~.
In those cases where the heat seal lacquer contains certain other components (particularly thermoset components such as epoxy resins), more significant increases in peel strength have been observed after curing. This indicates that the epoxy can flow into the pores and reinforce the weakened stratum.
Consequently, trial and experimentation with various adhesives can produce a range of peelable structures having a spectrum of actual peel strengths making the structures suitable for a variety of end uses.
The peelable structures (metal plus weakened anodic film) produced according to the present invention may be incorporated into sealed containers in order to permit such containers to be opened by peeling, but the way in 35 which the structures are incorporated into the containers can vary from case to case. For example, in the case of a shaped container having a hollow body provided with a flat W093/06992 ; PCT/CA92/~433 211891~ ~

rim to which a flexible foil lidding material is sealed to close ~he container, the peelable anodic oxide film may be formed on the lidding material itself (in which case the lidding material forms the peelable structure of the invention), which is then sealed to the rim by a layer of adhesive, or alternatively the peelable anodic oxide film may be formed on the rim of the container body (and/or other parts of the container body, if desired) and then an anodized or unanodized lidding material adhered to the rim 10 via an a & esive layer. The adhesive may be applied first to the container body or alternatively to the lidding material, or it may be introduced as a separate self-supporting sheet or wafer during the sealing process.
If the container is in the form of a pouch, the peelable anodic film may be formed on either one of two sheet-like members adhered together to form the pouch in order to allow the members to be peeled apart when ;~
desired.
Figs. 2 and 3 of the accompanying drawings illustrate in more detail the ways in which the peelable structures of the present invention may be incorporated into containers.
Figure 2 shows a partial cross-section of a container body 20 provided with a lid 10 incorporating a peelable structure according to one form of the present invention attached to a container rim 21. The lid 10 consists of an aluminum foil 11 having an overlying anodic film 12 on its lower side. The film has pores 14 extending from outer surface 15 and the inner end of the pores are provided 30 with branched pore regions 17 forming a weakened stratum 19 adjacent to the underlying surface 13 of the metal.
The lid consequently has the structure shown in Figure l(C) except that it is inverted.
The outer surface 15 of the anodic film 12 is adhered to the rim 21 of the container 20 by a layer of adhesive 22. The lid 10 extends beyond the rim 21 by a short distance to create a graspable tab 23. As the tab 23 is W093/06992 21 18 91 2 PCT/CA92/~33 , .
17 `
peeled away from the rim 21 in the direction of the arrow, separation takes place between the foil substrate ll and the anodic film 12 along the weakened stratum l9. Hence, no separation takes place at or within the adhesive layer 22 and the anodic film 12 (or at least its outer part) remains adhered to the rim 21 of the container after the remainder of the lid has been peeled from the container.
Figure 3 is a partial cro~s-sectional view similar to Figure 2 except that it shows a lid 11 having a ~tructure somewhat similar to that of Figure l(D) (except inverted).
In this case, the we~kened stratum 19 is formed adjacent to the outer surface 15 of the anodic film so that only a very thin outer layer 12a of the anodic film remains adhered to the rim of the container after the remainder of the lid material has been peeled away.
The peelable structures illustrated above make it possible to use a variety of adhesives for the adhesive layer 22 used to adhere the lid to the container rim, provided of course that the strength of the adhesive is such that separation takes place along the weakened stratum 19 rather than at or within the adhesive layer 22.
Accordingly, specialized peelable adhesive formulations or blends may not have to be employed, and more common and less expensive adhesives may be used instead.
Furthermore, since the peel strength of the lidding material is substantially constant, the same lidding material can be used to seal containers of different kinds, sizes, and compositions while still imparting a suitable peel strength.
Although the structures shown in Figures 2 and 3 employ a layer 22 of ~h~sive or lacquer for attachment of the lidding material lO to the container rim 21, it is also possible to use a layer of heat-sealable material to attach the lid to the container rim. A polyester or other plastic that softens when heated and flows to some extent into the pores 14 and into minute cavities in the rim 21 can be used for this purpose. The heat-sealing material :
w093/06992 PCT/CA92/~433 2~8~12 22 may be applied to the anodic film 12 in advance of the attachment of the lid to the container using st~nd~rd heat-seal laminating techniques. To seal the resulting lidding material to the container, heat and pressure is required in order to cause the material to flow in the desired manner.
The foil 11 is normally a lidding gauge and grade of aluminum foil. Since the anodizing procedure to impart peelability is required only on one side of the foil, foil 10 which is lacquered or laminated to plastic on the opposite side may be used. Alternatively, the anodization may be carried out in such a way that only one side of the foil material is anodized. However, it is easier on a commercial scale to anodize both surfaces of the foil and to provide the weakened stratum only on one of those surfaces. This makes subsequent printing on the outsides of the lid easier because porous anodized films form good substrates for printing (particularly when the anodization is carried out in phosphoric acid). Usual pretreatments required for printing can thus be avoided. Before anodization is carried out, the foil is usually subjected to the normal degreasing and rinsing procedures.
The anodization and voltage reduction procedures described above are then carried out, normally in such a way that the porous oxide film thickness is quite low (preferably less than about lx104 cm rl micron]).
After the pore reduction process has been completèd, a short period of soaking of the foil in the electrolyte will cause some pore wall dissolution. This results in the desired weakening of the metal-oxide interface.
After the period of soaking, and after further normal anodization if this is carried out, the anodized foil is thoroughly rinsed and dried and then the adhesive layer 22 is applied to the outer surface of the anodic film.
Since a thin layer of oxide (12 or 12A) is left on the adhesive 22 after removal of the remainder of the lidding material, a message originally printed on the W093/06992 ~ 9 ~ 2 PCT/CA92/~433 . i . 19 outer surface of the oxide shows up clearly on the surface of the lid rim once the lid has been removed. This is difficult to do when conventional lidding materials are used because the adhesive layer obscures any message 5 printed on the container rim. Examples of such messages include company slogans and logos, promotional messages, recycling reminders, lottery numbers, etc.
It has been found that the peelable anodic film required in the present invention can be made so thin, lO while still remaining effective, that the films generate visible colours by optical interference effects. For this to occur, as disclosed for example in our copending European patent application Serial No. 90303069.0 filed March 22, 1990 and published on September 26, 1990 under 15 publication No. EP 0 389 274 A2, it îs normally necessary to coat the surface of the anodic film with a discontinuous layer of metal so thin that it is translucent. This can be done, for example, by sputtering. Moreover, the anodic film must be "optically thin", i.e. less than 3x10-4 cm t3 microns] and preferably less than lx104 cm [1 micron~. Such interference colours may be visible, when the anodic film is used in a structure according to the present invention, if a part of the container or the sealing element are made of 25 transparent material, e.g. transparent plastic or glass.
In the region where the container or package seal is formed, the adhesive enters the pores of the anodic film and alters the optical properties compared with the remainder of the film outside the seal area and thus a different colour or appearance is observable. When the sealing element is peeled from the container or package or when the sealing element becomes unattached in part of the seal area, a different visible colour or appearance is produced and this change of colour is irreversible. This 35 means that the generated interference colour can be used to indicate seal integrity or acts as evidence of tampering. Coloured peelable structures produced in this W093/06992 PCT/CA92/~33 211~912 20 way are particularly useful for containers or packages ;
containing pharmaceuticals and foodstuffs.
A structure of this type is shown in Fig~ 4 of the drawings. In this structure a contain~r body 20 has a rim 21 made of a porous-anodization metal and a weakened anodic film 12 is formed on the rim. The film 12 is optically thin and has a translucent metal layer 25 formed on the outer surface of the film. A layer of adhesive 22 attaches a transparent flexible closure element 26 to the rim. Optical interference effects resulting from light reflected from the surface of translucent metal layer 25 a~d the underlying rim 21 result in the generation of a visible colour which can be seen through the flexible closure element and the adhesive layer 25. The 15 penetration of some of the adhesive 25 into the pores causes the color to be different in the sealed region ~han in unsealed regions of the rim or other parts of the ~`
container body provided with the coloured structure.
Separation along the weakened stratum 19 causes the 20 generated colour to be lost, thus indicating a loss of effective sealing of the container. The colour cannot be regenerated by re-attaching the previously detached anodic film 12 to the rim 21.
Although the peelable structures of the present invention have been described above with reference to their use for the formation of peelable sealed containers, the peelable_structures of the present invention may also be used in metal foil/polymer laminates of the type commonly used, for example, in the packaging industry.
For example, an aluminum foil having an anodic film containing a weAkçned stratum may be attached by means of an adhesive or by direct heat-sealing to a polymer film made, for example, of polypropylene or other suitable polymer. Other laminating processes, e.g. extrusion coating, may be employed, if desired. A cross-section of a laminated packaging film proA~lc~ in this way is shown in Fig. 5, in which 50 is a metal foil, 51 is an oxide W093/06992 21~ 8 91 ~ PCT/CA92/00433 film having a weakened stratum 52, and 53 is a polymer layer. The polymer layer 53 can be peeled from the metal foil 50 along the weakened stratum 52, when desired.
In these products, the anodic film should be produced -s in such a way that the peel strength is sufficient to prevent delamination of the structure during normal use, but low enough to permit deliberate delamination during recycling. ~ormally, the peel strength falls in the range of 0.3 to 10 N/cm and more preferably 1.5 to 5 N/cm (for 10 peeling at a constant 180- angle).
These foil/polymer laminates are recycled in different ways according to the materials employed and the stage of use. For example, when shapes, such as lids etc., are stamped from sheets of the laminates to leave -continuous webs of scrap, it is possible to continuously peel apart the polymer layer from the metal foil to give readily recyclable sorted scrap. The foil itself is uncontaminated and the polymer film is left with a very thin (e.g. O.lx104 cm ~0.1 micron]) layer of porous oxide 20 attached to one surface. With this level of a relatively inert oxide, the polymer film may be re~-~u-.d and recycled into useful products, bearing in mind that, for a lOx10-4 cm [10 micron] polymer film, the oxide would represent less than 1% by volume. Inorganic fillers of much higher 25 volume fractions are commonly used in the plastics industry (e.g. talc is a commonly used filler in poly-propylene to reduce the cost and give a white coloration).
In the case of laminates which have been used by theconsumer, separation of the layers may be carried out either by the consumer or by a commercial recycling facility. In the latter case, it may be possible (e.g.
by a cryogenic process) to separate the metal from the polymer more effectively than for normal, adhesively bonded laminates.
In the former case, it is possible to design packages so that the consumer separates the foil from the plastic.
In addition to recycling, there may be other reasons W093/~992 PCT/CA92/00433 22 ~
why metal/polymer laminates should be separable. For example, in some packaging applications, a foil layer is provided for its barrier properties but needs to be removed prior to microwave heating. Similarly, there may be applications where it is necessary to remove a foil layer to expose an underlying plastic film which itself has desired functional properties (e.g. a controlled release membrane for an air freshener).
If desired, the process of forming peelable structures according to the present invention may be carried out on a continuous basis in an apparatus of the type shown in Fig. 5. The equipment 30 consists of a tank 31 separated into individual compartments 3lA into which an electrolyte may be fed via inlet tubes 32. A first series of rollers 33 is positioned above the tank 31 and a second series of rollers 34 is positioned within the tank 31 near the bottom of each compartment 31A. The rollers are so positioned with respect to each other that a flexible aluminum f¢il web 35 may be carried over one of the upper rollers 33, moved downwardly through the first compartment of tank 31, carried over one of the lower rollers 34 and moved upwardly through the compartment.
This is repeated until the initial section of foil web 35 has completed several (in this case 10) vertical passes through each compartment of the tank, whereupon the web exits the tank. Two anodes 36 in the first tank compartment and two cathodes 37 in each of the subsequent tank compartments are positioned vertically, adjacent to the vertical runs of the web. The anodes and cathodes are connected to a power supply in such a way that the voltage between the catho~Ps and the foil (anode) can be varied in each tank, or as required to effect the voltage reduction procedure necessary to produce pore we~kening, as previously described. The movement of the foil through the tank is controlled at such a speed that a suitable length of time is spent by the foil in each of the tanks and a final 50~ki nq period takes place in the final runs 2118912 ;
, .. .. ,.. ~ .

of the web unde~ very low (typically lV or less) voltage.
After emerging from the tank, the foil web 38 is rinsed to remove traces of the acid electrolyte and is then dried.
An adhesive layer or heatosealed polymer film may be applied to the side of the foil having the anodic film provided with the weakened stratum, if desired.
The invention is illustrated in more detail in the Examples provided below. These Examples are provided for -the purpose of illustration of the invention rather than limitation of the scope of protection.

A sample of annealed bright aluminum foil (70x104 cm ~70 microns]) was anodized in lM H3PO4 at 30'C and 15V for 3 minutes. The voltage was then stepwise reduced (0.5 every 6 seconds) to OV, and held there for 55 secon~c.
After rinsing and drying,the foil was coated with a thin layer of MorprimeR lOB adhesive (polypropylene dispersion in an organic solvent), cured at 200-C, and heat sealed to an aluminum/polypropylene container filled with water. A
second sample, also anodized at 15V for 3 minutes without the voltage ramp-down and soak at OV, was similarly coated and heat sealed to a container. Neither sample leaked after heat sealing. However, the second sample was extremely difficult to peel and ended up tearing in a region removed from the seal, while the first sample with the voltage ramp-down peeled very well, transferring the weakened_oxide from the foil lid to the container rim.

Thinner films (5V/2 min, lM H3P04 at 30 C with a soak 30 time of 40 seconds where used and lOV/30 sec, lM H3P04 at 30-C with a soak time of 30 seconds where used) were also prepared with and without weakened oxides and sealed to water-filled containers. Small holes were cut in the lids and the samples were than placed in an autoclave for thirty minutes at 121-C and 15 psi to simulate retorting.
No leaking was observed from any of the seals of the containers after this treatment. Again, the samples with W093/~992 ` PCT/CA92/00433 the weakened oxide film exhibited the best peeling behaviour.

A sample was prepared having a weakened zone at the top of the oxide film rather than at the metal/oxide interface. Here, anodizing was done in lM H3P04 at 30-C by ramping the voltage up to lOV and immediately bringing it down step-wise to OV. After a brief soak (lo seconds) in the electrolyte at OV, the voltage was once again ramped 10 up to lOV for 120 seconds to re-anodize below the branched pores. After applying adhesive and curing it, the foil was heat-sealed to a polypropylene/aluminum containèr and peeled. The lid appeared to release at this oxide/oxide interface, transferring the branched pores and adhesive to the container rim and leaving the major pores bPhin~ on the lid stock.

Samples were prepared by anodizing 70x104 cm ~70 microns] aluminum foil in lM phosphoric acid at 15V and 30 C for 3 minutes to form a thin porous oxide film approximately 2000 Angstrom thick. The oxide film/metal adhesion was weakened by reducing the voltage in steps to oV and allowing sufficient time for the current to recover after each voltage reduction. A final soak was carried out for 55 seconds. A layer of aluminum (250 Al~y~oms thick) was then deposited on top of the porous oxide by magnetron sputtering, resulting in a thin film interference colour. Following sputtering, the surface of the foil was ~oated with Norland optical grade adhesive, and a transparent polymer film or thermoformed shape was bonded to the foil on curing of the adhesive in a W oven.
When the polymer component was peeled from the aluminu~
foil, the colour was lost in the sealed regions.

A variety of oxide films were formed on aluminum foil at various voltages and the films were allowed to soak in the electrolyte at zero volts for various periods of time.
.

W093/06992 21 ~ 8 912 PCT/CA92/00433 . . .

All of the anodization procedures were carried out at 300C
in lM H3PO4, using a 60 second soak time at peak voltage.
The anodized foils were coated with Morprime lOBR adhesive and heat-sealed to ALUCONR 250120F containers. The peel strengths of the resulting structures were measured at a constant 90 angle and the results (an average of the results from two samples prepared under each set of conditions) are summarized in the Table below:

TABLE

PEEL STRENGTH VERSUS SOAK TIME/ANODIZING VOLTAGE

(V) (S) (N) 11.1 10.2 10.2 12.9 8.0 8.6 7.4 7.2

6.9 These results show that the peel strength is affected by the duration of the soak time at zero volts and by the anodizing voltage. Longer soak times generally result in lower peel strengths and lower voltages result in higher peel strengths.

Samples of 70x104 cm t70 microns] aluminum foil were anodized at lOV in lM H3P04 at 60-C for 2 seconds following 30 which the voltage was reduced in stages to lV or less over the course of 12-14 seconds and then the foil was allowed to soak at lV or less for 2-6 seconds. In this case, it W093/06~2 ~ PCT~CA92/~33 211~912 is not necessary to include an additional soak at zero volts. The carryover electrolyte wets the foil for a short time prior to rinsing, and thereby will provide the final weakening. These conditions of voltage, time, temperature and electrolyte concentration were chosen to best simulate continuous production of lidstock with a peelable oxide layer. The anodized foils were sealed to ALUCONR 350120F containers as described in previous Examples and it was found that small variatlons in the early stages of the voltage ramp-down sequence did not have a pronounced effect on peel strength, the peel strength being mainly controlled by the final stages and the soak stage. The average peel strength (measured at a constant 90- angle) of 45 samples was 9.01N, the majority falling within the range defined as peelable for the cont~iner and test configuration, i.e. 8-12N. It is to be noted that this Example makes use of the incomplete recovery procedure mentioned above.
INDUSTRIAL APPLICABILITY
The present invention can be used to produce sealable containers and packages of various kinAc that can be opened by peeling. Peelable laminates for packaging applications can also be formed.

Claims (31)

Claims:

1. A peelable structure suitable for attaching a metal layer to other layers of a laminated article, said structure including a substrate (11) having a surface (13), said substrate comprising a porous-anodizable metal at said surface; and a porous anodic film (12) overlying and attached to said surface (13); characterized in that said porous anodic film (12) has a weakened stratum (19) positioned between an outer film part and an underlying part including said substrate, said weakened stratum (19) being strong enough in use of said structure to prevent detachment of said outer film part from said underlying part, except by deliberate peeling of said structure along said weakened stratum (19).

2. A structure according to claim 1 characterized in that said anodic film (12) has a thickness in the range of 0.1x10-4 cm [0.1 micron] to 25x10-4 cm [25 microns].

3. A structure according to claim 3 characterized in that said anodic film (12) has a peel strength of about 8N-12N.

4. A structure according to claim 1, claim 2 or claim 3 characterized in that a polymer layer is bonded directly to said anodic film (12) and has a strength of attachment greater than the peel strength of said anodic film (12) at said weakened stratum (19).

5. A structure according to claim 1, claim 2 or claim 3, characterized in that a layer of adhesive (22) overlies and is attached to said anodic film (12), said adhesive having a peel strength greater than the peel strength of said anodic film (12) at said weakened stratum (19).

6. A structure according to claim 5 wherein said adhesive (22) partially penetrates said anodic film (12) and modifies the peel strength at said weakened stratum (19).

7. A structure according to claim 5 characterized in that said adhesive (22) is suitable for use with foodstuffs.

8. A structure according to claim 1, claim 2 or claim 3 characterized in that said substrate (11) is in the form of a flexible foil having a second flat surface opposite to said surface attached to said anodic film (12).

9. A structure according to claim 8 characterized in that a second anodic film overlies and is attached to said second flat surface.

10. A structure according to claim 1, claim 2 or claim 3 characterized in that said anodic film (12) containing said weakened stratum (19) is a film produced by anodizing a surface of a porous anodizable metal in an electrolyte and at a voltage which results in the formation of a porous anodic film, continuing said porous anodization while carrying out a voltage reduction procedure in order to introduce a weakened stratum into said anodic film, and allowing said film to stand in said electrolyte or other acidic solution for a period of time to further weaken said film along said stratum, wherein said voltage and said period of time are made such that, under the conditions employed, said weakened stratum is strong enough in use of said structure to prevent detachment of said outer film part from said underlying structure, except by manual peeling of said structure along said weakened stratum.

11. A peelable foil lidding material suitable for closing a sealable container, including a flexible metal foil (11) comprising a porous-anodizable metal at a surface (13) of said foil, and a porous anodic film (12) overlying and attached to said surface (13); characterized in that said porous anodic film (12) has a weakened stratum (19) positioned between an outer film part and an underlying part including said metal foil (11), said weakened stratum (19) being strong enough in use of said lidding material on a container to prevent detachment of said outer film part from said underlying part, except by manual peeling of said lidding material from said container.

12. A material according to claim 11 characterized in that a layer of adhesive (22) overlies and is attached to said anodic film (12), said adhesive having a peel strength greater than the peel strength of said anodic film at said weakened stratum (19).

13. A material according to claim 11 or claim 12 characterized in that said anodic film has a peel strength of 8-12N.

14. A sealed container comprising a hollow body for holding an object to be contained and a flexible closure element attached to said container body, said sealed container having a peelable structure positioned between said closure element and said container body, said peelable structure including a substrate (11) having a surface (13), said substrate comprising a porous-anodizable metal at said surface and a porous anodic film (12) overlying and attached to said surface characterized in that said porous anodic film (12) has a weakened stratum (19) positioned between an outer film part and an underlying part including said substrate, said weakened stratum (19) being strong enough in use of said structure to prevent detachment of said outer film part from said underlying part, except by manual peeling of said flexible closure element from said container body.

15. A container according to claim 14 characterized in that a layer of adhesive (22) attaches said flexible closure element to said container body and overlies said anodic film of said peelable structure, and in that said adhesive has a peel strength greater than the peel strength of said anodic film (12) at said weakened stratum (19).

16. A container according to claim 14 characterized in that said anodic film (12) has a peel strength of 8-12N.

17. A sealed container according to claim 14, claim 15 or claim 16 characterized in that said porous anodic film (12) is optically thin and is provided at an outer surface of said film with a translucent reflective metal layer so that light reflected from said substrate and said translucent metal layer generates a visible colour, and in that one of said flexible closure element and said body is transparent to permit viewing of said colour therethrough.

18. A container body having a rim area suitable for receiving a flexible closure element for closing said container body, said rim area incorporating a peelable structure for attachment to said closure element including a substrate (11) having a surface (13), said substrate comprising a porous-anodizable metal at said surface; and a porous anodic film (12) overlying and attached to said surface (13); characterized in that said porous anodic film (12) has a weakened stratum (19) positioned between an outer film part and an underlying part including said substrate, said weakened stratum (19) being strong enough in use of said structure to prevent detachment of said outer film part from said underlying part, except by peeling of said flexible closure element from said container body.

19. A container body according to claim 18 characterized in that a layer of adhesive (22) attaches said flexible closure element to said container body and overlies said anodic film (12) of said peelable structure, said adhesive having a peel strength greater than the peel strength of said anodic film (12) at said weakened stratum (19).

20. A container according to claim 18 or 19, characterized in that said anodic film has a peel strength of 8-12N.

21. A peelable flexible laminated sheet material, which comprises a flexible layer (50) of anodizable metal; a flexible porous anodic film (51) of metal oxide overlying a surface of said metal layer, and at least one flexible polymer layer (53) attached to said anodic film;
characterized in that said anodic oxide film includes a weakened stratum (52) and in that the strength of said film along said weakened stratum is such that separation of said at least one polymer layer and said metal layer is prevented during normal use of said film as a packaging material, but such that said at least one polymer layer and said metal layer may be separated by deliberate peeling apart of said layers.

22. A material according to claim 21 characterized in that said anodic film has a peel strength of 8-12N.

23. A process for producing a peelable structure suitable for attaching a metal layer to other layers of a laminated article, said process comprising anodizing a surface of a porous anodizable metal in an electrolyte and at a voltage which results in the formation of a porous anodic film;
continuing said porous anodization while carrying out a voltage reduction procedure in order to introduce a weakened stratum into said anodic film; and allowing said film to stand in said electrolyte or other acidic solution for a period of time to further weaken said film along said stratum; characterized in that said voltage and said period of time are made such that, under the conditions employed, said weakened stratum is strong enough in use of said structure to prevent detachment of said outer film part from said underlying structure, except by manual peeling of said structure along said weakened stratum.

24. A process according to claim 23 characterized in that said anodizing step is carried out at a voltage in the range of about 5-15 V.

25. A process according to claim 23 characterized in that said anodizing step is carried out at a temperature in the range of about 40-60°C.

26. A process according to claim 23 characterized in that said anodizing step is carried out in an electrolyte containing about 1M phosphoric acid.

27. A process according to claim 23 characterized in that said anodizing step is carried out for a period of about 20-30 seconds.

28. A process according to claim 23, claim 24, claim 25, claim 26 or claim 27, characterized in that said voltage reduction procedure involves a reduction of voltage in steps or continuously at a rate in the range of about 0.2-2 volts per second to a final voltage of about 1V or less.

29. A process according to claim 23, claim 24, claim 25, claim 26 or claim 27, characterized in that said film is allowed to stand in said electrolyte or other material for a period of approximately 2 seconds.

30. A process according to claim 23, claim 24, claim 25, claim 26 or claim 27, characterized by coating said anodic film with a layer of adhesive, having a peel strength greater than a peel strength of said anodic film at said weakened stratum.

31. A process according to claim 23, claim 24, claim 25, claim 26 or claim 27 characterized by bonding a polymer layer directly to said anodic film.