Tamper evident closure with colour change system

Abstract: An irreversible tamper evident system is provided by a color change system (32) carried by the flexible button portion (24) of the closure (10). A color change system (32) comprises an indicator coating (36) over a dark colored substrate coating (34). The indicator coat (36) is suitably colored with a light colored transparent colorant such as an orange colored fluorescent dry. The indicator coat (36) is also preferably a liquid material which can be cured by evaporation, heat, UV irradiation or the like, to form a solid layer. When the substrate layer (34) and indicator layer (36) are in intimate contact, a first color is observed. Depending upon the relative colors used for this substrate and indicator layers (34, 36) this first color can be a combination of the colors of the two layers (34, 36) or can be primarily the color of the substrate layer (34). However, when the layers (34, 36) become separated and the indicator or outer layer (36) is spaced from the substrate inner layer (34) a second color is observed. The second color is primarily the color of the indicator coat (36).

Description: The present invention generally relates to closures having end panels of which at least an area is formed to flex when the closure is applied to a container and, more particularly, to a closure wherein the flexible area of the end panel is provided with an irreversible tamper indicating system which is actuated when the flexible area of the end panel flexes from a sealed condition to an unsealed condition. Among the various closures made for the food and beverage industry is a "button" or "pop top" closure wherein the closure contains a flexible portion which assumes a given flexed position to indicate a sealed package and a different position when the package seal is breached. These "button" or "pop top" closures are commonly used in vacuum sealed food products such as baby food products to warn purchasers when the vacuum condition under which the food was packaged has been breached. Although closures having tamper indicating buttons are predominantly in use in vacuum applications, there also have been more recently developed closures with buttons which are mechanically actuated so as to move from an as formed "down" position to an upwardly projecting "up" position when the closure is properly applied to a container. In this "up" position the closures are further characterized as having energy stored within the closure end panels urging the buttons to their as formed "down" position. Removal of these closures from the containers associated therewith results in the buttons moving to their as formed "down" position due to the release of the energy stored within the end panels. Closures having end panels incorporating tamper indicating buttons are used extensively for the food industry, especially for vacuum packaged product, because they are effective quick-detection means that lets one know some very important conditions about the container. Typically in vacuum applications, when the container is properly sealed and a vacuum exists therein, the button is in a "down" position while when the container has been opened and the closure reapplied, or the vacuum within the container otherwise lost, the button will be in its "up" position. Additionally, in vacuum package applications, when the closure is first opened and the vacuum is lost, a hissing sound may be heard. Through the extensive commercial use of such button closures, the purchasing public has become generally aware that if the deflectable section of the button is up then the original seal has been broken and that the container should be rejected. Additionally, in the case where the button closure is used in conjunction with a vacuum package container, the purchasing public has been sensitized to listen for a hiss of air or a "popping" sound to determine whether or not that container has been previously opened. The popping of the top and, in the case of a vacuum packaged product, the sound associated with the loss of vacuum are indicating means to warn purchasers when the integrity of the package has been breached. These indicators, however, are not fool proof and can be intentionally overridden. For example, it is known that a button closure for a vacuum packaged product can be returned to its "tamper free" state even after the package has been opened. This is accomplished by merely heating the open container and when the container is hot, recapping the closure. This procedure will recreate the vacuum seal and reset the button. Separate tamper evident means have been used in association with button caps to augment the flip or pop of the button. For example, button caps, and other screw top closures, are often used in association with a shrink wrap. Also, the button cap may be provided with a band at its base, joined to the remainder of the cap through a line of weakness. The band is prevented from rotating or from rising up the screw thread when the cap is unscrewed, and as a result, upon closure opening, the band becomes detached from the remainder of the cap. The packaging industry has also recognized the desirability of providing a visual means to determine whether the integrity of a sealed container has been breached. For example, U.S. Patent No. 3,736,899 (Manske) is directed to a pressure change indicator. The '899 patent discloses a button type cap having a flexible panel with a reflective surface and a disk-like element which covers up all or most of the flexible panel when the panel is flexed inward but which provides a gap around the periphery of the panel when it is flexed outward. The gap reveals a highly visible or contrasting color which is seen on the flexible panel either by means of a color on the panel itself or a color on the underside of the disk-like member. The pressure change system of the '899 patent apparently may be reestablished by recreating the vacuum in the package and, accordingly, in such a case would not be irreversible. U.S. Patent No. 4,429,803 (Butterfield) is directed to tamper evident means for multiple dose medical vials of the type having a rubber seal closure. The tamper evident means of the '803 patent is a blister-like sac containing a harmless dye. According to the '803 patent, the blister-like sac will release the dye and thereby color the remaining contents of the vial when the vial's seal is broken. U.S. Patent No. 4,511,052 (Klein et al.) is directed to a tamper indicating seal for a container. According to the '052 patent a frangible envelope containing an indicator is attached to the band and neck of the container having a closure so that when the closure is opened the frangible envelope will rupture and expose the indicator. The indicator can be a chemical substance which undergoes a change in color when exposed to the atmosphere such as an oxygen or moisture sensitive substance. U.S. Patent No. 4,526,752 (Perlman et al.) discloses a tamper evident package incorporating an oxygen sensitive leuco dye. According to the '752 patent, the oxygen sensitive leuco dye is sealed within the package in an anaerobic environment. The package can have a transparent cap through which the oxygen sensitive leuco dye is visible to show the integrity of the package. If oxygen is admitted to the package such as by opening the package, the dye will undergo a color change. U.S. Patent No. 4,813,712 (Scopes) is directed to providing a visible indication of whether a button cap is in its concave or convex form. According to the '712 patent the condition of the button can be determined by applying a pattern to the button surface which pattern can display one visible form when the surface is concave and a different visible form when the surface is convex. The different visible forms can include two different colors. In this regard, the '712 patent discloses a button cap having an embossed pattern wherein the pattern displays one color when in a given orientation such as concave and displays a different color when the orientation changes such as to convex. In another embodiment, the pattern is formed of superimposed layers which are displaced relative to one another when the surface changes between its concave and convex forms. Either the layers or the substrate for the layers contains a grid pattern which provides the closure with different appearances in the concave and convex forms. As noted in the '712 patent, a high degree of accuracy is required in laying down the patterns to ensure the colors register correctly with the embossed pattern to produce the desired visual result. Additionally, the surface indicating systems of the '712 patent appear to be reversible. U.S. Patent No. 4,877,143 (Travisano) is directed to a closure such as a button cap wherein the button carries an indicator such as a color or an imprinted word like "open" thereon. The indicator is covered with a translucent layer having a light diffusing surface which is provided by a Fresno lens. When the button is in the sealed position, the indicator is drawn away from the translucent/light diffusing layer which results in the indicator being obscured so that it cannot be seen through the translucent layer. When the container is opened and the button flips, the indicator is brought into contact with the translucent layer and the indicator becomes visible therethrough. Similar to the '712 (Scopes) patent above, the tamper evident system of the '143 patent appears to be a reversible system rather than an irreversible system. International patent application WO92/00891 relates to a colour change system to be incorporated in a flexing area of an end panel of a closure. The colour change system includes a dark background coating on a flexing portion of the end panel to which there is bonded by way of an adhesive a brittle layer which, due the flipping action of the flexing portion of the end panel, will fracture. The brittle layer is preferably of a light colour and is coloured using fluorescent dye. The combination of the background colour and the fluorescent colour of the brittle layer produces a first colour in the original closure and when the end panel flexes and the brittle layer fractures to not only crack but also tear apart, to reflect its own light colour more brilliantly, the colour of the colour change system drastically changes to indicate tampering. Despite recognition of the need for tamper proof or tamper evident button closures, and responsive efforts related thereto there still exists the need for an improved tamper evident button closure. In a first aspect, the present invention provides a container including a container body and a removable closure sealingly applied to said container body, said closure including a flexible end panel portion having formed therein a sealing state indicating area which can flex from a seal indicating position to a non-seal indicating position due to the release of energy stored within said end panel, said sealing state indicating area carrying an irreversible tamper indicating color change system comprising an effectively dark coloured base layer, and a translucent light coloured indicator layer, characterised in that the container includes a photo degradable bonding/release layer interposed between said base layer and said indicator layer, said photo degradable bonding/release layer having been partially degraded after application so as to weaken the attachment of said bonding/release layer to said base layer and said indicator layer, whereby when said flexible end panel is in a seal indicating position said degradable bonding/release layer maintains said base layer and said indicator layer in effective intimate contact with each other so that when viewed through said indicator layer said color change system has an effective first color, and when said flexible end panel flexes to its non-seal indicating position, said bonding/release layer is broken such that said indicator layer separates from said base layer and said color change system when viewed through said indicator layer has a second color different from said first color. The present invention provides an irreversible tamper indicating system for use in conjunction with closures having deflectable end panel areas such as button closures. The irreversible tamper indicating system of the present invention comprises a system which undergoes an irreversible change in color upon deflection of the end panel area such as the flipping of the button of a button cap. The color change system comprises the superimposition of differently colored coatings such as an indicator coating of a first color and a background coating of a second color. Preferably, the indicator coating is a translucent coating containing a light colored colorant and the base coating contains or covers a dark colored colorant. The indicator coating and base coating are placed in intimate contact, either directly or indirectly through intervening coatings such as an adhesive coating, with each other on the surface of closure. When the two coatings are in intimate contact with each other a first color is perceived which is different from the individual color of the indicator coating. In this regard, without being limited to any theory of the invention, it is believed that when the indicator coating and background coating are in intimate contact with each other the perceived color results in large from light which passes through both the indicator coating and base coating and which is reflected back through those coatings. In accordance with general physical principles, the color perceived is a composite of the colors of the indicator coat and background or base coat which is a function of the absorbance of the light passing through each layer which in-turn is dependent upon the color of the colorants, the concentration of the colorants and the thickness of the coats. In embodiments of the present invention, when the flexible portion of the end panel of the closure incorporating the color evident system of the present invention flexes upon opening of the container, the flexing action actuates a color change by causing the indicator coat to separate from the base coat. When the indicator coat separates from the base coat, a reflection boundary or reflective interface is formed which causes a greater portion of light to be reflected at, as opposed to passing through, the lower surface of the indicator coat. Accordingly, the perceived color is principally the color of the indicator coat rather than a composite color of the indicator coat and base coat. In embodiments of the present invention, the color of the system is determined by the adhesion, or lack thereof, between the indicator coating and button coating. In practice, such as when used for food products, when the sealed container leaves the food packer, the indicator and base coatings are in intimate contact with each other. For practical reasons, the adhesion between the indicator coat and base coat should be sufficient to withstand inadvertent, but tamper free, contact such as that which may occur during transportation and stocking of the product without unintentional separation of the coatings. On the other hand, the adhesion between the indicator coating and button coating must be weak enough so that the flipping action of a button closure can activate the tamper evident system by causing a sufficient loss of adhesion between the indicator coating and base coating. In embodiments of the irreversible aspect of the present invention, the coatings must be selected so that once the initial intimate contact between the indicator coating and base coating is broken, it can not be reestablished. An indicator coating that can be readhered to the base coating by drawing the button back down, heat massaging or any other method could defeat the tamper evident feature of the present invention. Accordingly, preferably the indicator coating of the present invention is composed of a resin which can be irreversibly solidified or set. Resins, such as thermoset resins which can be irreversibly set such as by chemical reaction, heat or radiation are preferred. Once this type of indicator coat is fully cured and the intimate adhesion between it and the base coat is broken, such intimate contact cannot be reestablished. The indicator coating preferably includes a UV resin, a photo initiator, a colorant such as a fluorescent dye, flow agents, fillers or other desirable additives. The indicator coating is preferably prepared as a viscous liquid mixture which is spread over the base coating on the button area of the closure. Preferably, the indicator coating has a thickness of between 0.127 to 0.508 mm (5 to 20 mils). The indicator coat can then be cured such as by passage through a UV oven to convert the viscous liquid mixture into a solid indicator coat. Examples of materials which can be used for the indicator coating are UV curable acrylates such as acrylated epoxies, acrylated urethanes, acrylated monomers such as TMPTA or TMPTMA and cationically cured epoxies. In embodiments of the present invention, when the tamper evident system is activated the indicator coating becomes separated from the base coating. Therefore, the tamper evident system also preferably includes a flexible transparent coating which will seal the indicator coat to the closure and prevent the actuated delaminated indicator coat from falling off the closure into the container. The overcoat material is selected so that it does not restrict the flipping action of the button, or interfere with the adhesion or release properties of the indicator coat or with the visual appearance of the system. Examples of materials that work well for the overcoat layer include clear, low cross-linked density, acrylated urethanes, two part epoxy and urethane systems, and UV curable cationic systems. Additionally, clear tapes such as polypropylene and polyester films which can be bonded to the closure, such as with adhesives or by heat sealing, can work well as the overcoat layer. In an embodiment of the present invention, a translucent bonding/release layer is interposed between the base coat and indicator coat. In this embodiment, the bonding/release layer acts as a means to bond the indicator coat to the base coat on the button closure prior to the integrity of the closed container being breached. When the container is opened, the flexible end panel is actuated and imparts enough energy to cause the indicator coat to irreversibly separate either alone or along with the bonding/release layer from the base layer. In this embodiment, the indicator coating can be applied as before as a thermoset resin or the indicator coat can be comprised of a preformed colored translucent material such as a translucent plastic disk. Preferably, the bonding/release layer is a photodegradable adhesive. The photodegradable adhesive can be used to sufficiently bond the indicator coat to the base coat at the closure manufacturer's facility. The closure can then be applied to a container and the flexible end panel portion can be set such as by pulling a vacuum thereon during packaging. The closure can then be subjected to an appropriate amount of ultraviolet radiation in order to degrade and weaken the bonding/release photodegradable adhesive. Upon opening of the package, the vacuum seal panel is actuated which imparts enough energy in order to fracture the weakened adhesive and thereby irreversibly allow the indicator coat to separate from the base coat and effect a color change. Accordingly, it is a general object of the present invention to provide an improved tamper evident closure. It is another object of the present invention to provide an improved tamper evident button closure. It is another object of the present invention to provide an improved tamper indicating system in the form of a color change system. It is another object of the present invention to provide an irreversible tamper evident color change system for a closure which contains a flexible portion which assumes a given position to indicate a sealed package and a different position when the package seal is breached wherein in the sealed position the flexible portion has a first color and in the breach condition the flexible portion has a second color. These and other objects of the invention will be more fully understood from the following description of, by way of example only, an embodiment of the invention with references to the accompanying drawings. Brief Description of The Drawings Fig. 1 is a top plan view of a conventional prior art tamper evident closure incorporating a conventional safety button. Fig. 2 is a transverse vertical sectional view taken generally along the line 2-2 of Fig. 1 and shows the cross-section of the closure with the button in its "up" convex state. Fig. 3 is an enlarged fragmentary vertical section view of the central button portion which shows further details of an embodiment of the tamper evident system provided on the button including a dark colored substrate layer under a bonding/release layer under an indicator layer under a transparent cover layer. Fig. 4 is a schematic sectional view showing the manner in which the tamper evident system of the embodiment shown in Fig. 3 may be armed after the closure has been applied to a container and the button deformed by a vacuum within the container. Fig. 5 is an enlarged fragmentary section view through the button of Fig. 4 after the closure has been removed from the associated container and the button has flexed to its "up" position and the bonding/release layer has failed causing the indicator layer to separate from the substrate layer. Referring now to the drawings in detail, reference is first made to Figs. 1 and 2 which illustrate a typical metallic button closure. The closure is generally identified by the numeral 10 and includes an end panel 12 which has an upwardly and outwardly sloping peripheral portion 14 defining the downwardly opening channel 16. The end panel 12 terminates in a generally cylindrical skirt 18 which, in turn, terminates in an inwardly turned curl 20. In order that the closure 10 may be applied to a container (not shown) of the type including a neck finish having external threads, the skirt 18 and the channel 16 are lined with a suitable sealing compound 22. When the closure 10 is pressed down on a neck finish of a container, a seal between the closure 10 and the container is formed between that portion of the sealing compound 22 underlying the end panel 12 while an interlock is formed between the threads of the container by that portion of the sealing compound 22 which lines the skirt 18. The closure 10 is constructed in a manner wherein the end panel 12 is provided with a centrally located button generally indicated by the number 24. The button 24 includes a central post portion 26 surrounded by an upwardly sloping annular portion 28 which, in turn, is surrounded by an annular generally flat portion 30. Preferably, the button 24 is mechanically reformed after its initial formation to a state of compressive residual stress such as by mechanically reforming in the manner described in U.S. Patent No. 5,016,769. Referring now to Fig. 4, in particular, it will be seen that when a closure 10 is applied to a container and a vacuum is drawn within such container, the button 24 is drawn downwardly. In accordance with the preferred embodiment of the invention, by mechanically reforming the button 24 as the closure 10 is being formed, the button 24 has certain stored stresses which facilitate its being maintained in the "up" normally convexed position of Figs. 2, 3 and 5. When the button 24 is drawn down into the container as shown in Fig. 4, these compressive stresses increase and there is a high tendency for the button 24 to flip upwardly from its "down" concave position of Fig. 4 back to its original "up" convex position. Thus, when the closure 10 is removed from a container and the vacuum applied against the underside of the end panel 12 is released, the button 24 will flip, snap or pop upwardly to its original position. It is this flipping action of the button 24 that actuates the tamper evident color change system of the present invention. The present invention particular relates to a button enhancement color change system which, as shown in Fig. 3, is generally identified by the numeral 50 and which is applied to the button 24. The button color change system 50 is particularly constructed to specifically designate that the closure 10 has been removed from the container even if the closure 10 is again placed on the container in the sealed closed position and thus forms tamper evident means for the closure 10. Colorants for the indicator coat 54 include transparent fluorescent dyes such as commercially available Pylakrome Oil yellow, Pylakrome pink, Pylam white, Keyfluor blue, Day Glo marigold orange and Mobay yellow dyes, transparent non-fluorescent dyes such as commercially available Macrolex yellow, Macrolex red, Macrolex blue, and Macrolex orange dyes, and opaque non-fluorescent dyes such as commercially available green production ink, red production ink, blue production ink, orange production ink and yellow production ink dyes. The color of indicator coat 54 and the effective color of base coat 52 are chosen so that when the indicator coat 54 and base coat 52 are in intimate contact the color change system 50 has a first color and when the indicator coat 54 separates from the base coat 52 the color change system 50 has a second color. Preferably, colors are chosen for the effective color of the base coat 52 such as black and the indicator coat 54 such as orange/yellow so that when the base coat 52 and indicator coat 54 are in intimate contact the color change system 50 appears greenish (for "GO", safe or untampered) and when the indicator coat 54 separates from the base coat 52 the color change system 50 appears orangish or yellowish (for "CAUTION", unsafe or tampered). It has been found that the use of resins such as acrylated epoxies, acrylated urethanes and cationically cured epoxies which are capable of multiple stage curing when used to formulate the indicator coat 54 provide a tamper evident system for a closure 10 which can be produced at the closure manufacturer's site and can be then fully "armed" at the packaging site. As schematically shown in Fig. 3, the indicator coating 54 is partially cured such as by exposure to UV radiation effected by an appropriate UV source 58. Preferably, partial curing of indicator coat 54 is sufficiently effected to provide a relatively non-tacky but flexible solid. It will be appreciated, however, that the indicator coat 54 can be precured to lesser states such as somewhat tacky and even still wet states as desired. As shown in Fig. 3, a flexible transparent coat 62 is applied over indicator coat 54 to seal the indicator coat 54 to the closure 10, to protect color change system 50 during transit and storage and to prevent the indicator coat 54 from falling off closure 10 when the indicator coat 54 delaminates from the base coat 52. The transparent coat 62 is formulated so that it does not restrict the flipping action of the button 24 or interfere with the separation of the indicator coat 54 from the base coat 52 upon flipping of button 24 or interfere with the visual appearance of the color change system 50. As shown in Fig. 3, the colour change system 50 in this embodiment of the invention, comprises a translucent bonding/release layer 56 interposed between a base coat 52 and an indicator layer 54. Base coat 52 either contains a colorant or is translucent and overlies a colored background coat 53 on the button 24 and base coat 52 is formulated to adhere to the surface of the button 24 and move with the button 24 without separation from the button 24. The indicator layer 54 is translucent and either inherently has a colored appearance or is formulated to include the colorant. In accordance with the principles of the present invention, the color of the indicator layer 54 differs from the effective color of the base coat 52. The bonding/release layer 56 is interposed between the indicator layer 54 and the base coat 52 to bond the indicator layer 54 to the base coat 52 in an effective intimate contact relationship prior to the breach of the integrity of a container sealed with a closure incorporating the color change system 50. In accordance with the objects of the present invention, the bonding/release layer 50 is translucent so that when the indicator layer 54 and the base coat 52 are in effective intimate contact, the perceived color of the color change system 50 is a function of the combined colors of the layers comprising the color change system 50. It will be appreciated that the indicator layer 54 can be made from resins such as acrylated epoxies, acrylated urethanes and cationically cured epoxies which are capable of multiple stage curing or the indicator layer 54 can be comprised of a preformed colored translucent material such as a color translucent plastic disc or a colored translucent plastic film. As shown in the embodiment of the invention depicted in Fig. 10, the indicator layer 54 can be applied to the button 24 over the bonding/release layer 56 while the button 24 is in its up concave configuration. Application of the indicator layer 54 while the button 24 is in its up position allows the color change system 50 to be applied to a closure at the closure manufacturer's facility. In accordance with the principles of the present invention, the bonding/release layer 56 is appropriately formulated and applied to a closure so that indicator layer 54 and base coat 52 are in effective intimate contact when the button 24 assumes it downward concave vacuum drawn position as shown in Fig. 11 and so that indicator layer 54 irreversibly separates from the base coat 52 when the button 24 flips back to its original "up" position as shown in Fig. 12. Suitable materials for the bonding/release layer 56 include photodegradable adhesives including relatively high molecular weight polymers which can be degraded such as by subjection to UV radiation to reduce or weaken their adhesive properties. Prior to degradation, the photodegradable adhesive can be used to sufficiently bond the indicator layer 54 to the base coat 52 during application of the color change system 50 to the button 24 and the arming of button 24 such as by pulling a vacuum thereon during packaging. It will be appreciated that if a UV curable composition is utilized for the indicator layer 54 and a photodegradable adhesive is utilized for the bonding/release layer 56 that it may be desirable to utilize photoactivators for the indicator layer 54 (e.g. photoinitiator(s) which actuates curing of the composition) and for the bonding/release layer 56 (e.g. photoabsorber which actuates degradation of the compositon) which are actuated by different wavelengths or mechanisms. Using different photoactuators for the indicator layer 54 and for the bonding/release layer 56 may be especially desirable to prevent premature degradation of the bonding/release layer 56 when the indicator layer 54 is being exposed to a UV source to fully cure indicator layer 54. Fig. 11 shows the closure 10 carrying the color change system 50 after the closure 10 has been applied to a container and the button 24 has been drawn down to its concave position by a vacuum within the container. As schematically shown in Fig. 11, the photodegradable bonding/release layer 56 can be degraded to weaken its bonding ability such as by exposure to UV radiation effected by an appropriate UV source 58. For example, it has been found that a photodegradable polystyrene resin such as commercially available Ecolyte PS-2005 resin supplied by Novacor of Leominster, Massachusetts has certain adhesive properties at its starting molecular weight of 111,000 M n and that after exposure to 12-13 Joules/cm 2 of UV energy it is degraded to a molecular weight of 86,000 M n and its adhesive properties are concomitantly reduced. As illustrated in Fig. 5, when the closure 10 incorporating color change system 50 is removed from a container and the vacuum applied against the underside of the end panel 12 is released, the button will flip, snap or pop upwardly to its original position. This flexing action of the button 24 is sufficient to disrupt the adhesive ability of the weakened bonding/release layer 56 thereby allowing the indicator layer 54 to separate from the base layer 52. As illustrated in Fig. 5, the adhesive failure of the bonding/release layer 56 results in the creation of a reflective interface or reflection barrier 60 between the indicator layer 54 and the base coat 52 which causes the color change system 50 to undergo a change in color. As shown in Figs. 3-5, the color change system 50 can include a flexible transparent coat 62 which is applied over indicator layer 54 to seal, the indicator layer 54 to the closure 10, to protect the color change system 50 during transit and storage and to prevent the indicator layer 56 from falling off the closure 10 when the bonding/release layer fails and indicator coat 54 separates from the base coat 52. Examples of materials that can be used to formulate the transparent coat 62 include clear, low cross-linked density, acrylated urethanes, two part epoxies and urethanes, and UV curable cationic systems. Additional materials that can be used for transparent coat 62 includes transparent tape such as clear polypropylene or polyester films which can be bonded to closure 10 such as by adhesively fixing or heat sealing the ¾ film to closure 10. Preferably, a material which reduces the interfacial tension or bonding between the indicator coat 54 and the transparent coat 62 is present between such coats to prevent the transparent coat 62 from interfering with the separation of the indicator coat 54 from the base coat 52. Such materials include surface active agents like soaps or soap solutions and other surfactants, waxes and other lubricants such as amides and stearates and the like, which can be applied to the indicator coat 54 prior to application of the transparent coat 62. It will be appreciated that the curable compositions used for color change system 50 such as the UV curable indicator coat 54 and UV curable transparent coat 62 may contain different curing agents and different amounts of curing agents to control the nature and degree of curing. For example, a UV curable indicator coat 54 composition may contain different photoinitiators which can be activated by different UV wavelengths to facilitate multiple stage curing of the indicator coat 54. Additionally, when a UV curable transparent coat 62 is used in association with a UV curable indicator coat 54 it may be desirable to utilize different photoinitiators in the indicator coat 54 and the transparent coat 62 so that each of the coats can be cured independently of each other and so that the cure of the transparent coat 62 does not untimely cure or otherwise interfere with the cure of the indicator coat 54. It will, of course, be appreciated that, if necessary, different UV sources and/or different UV lamps may be used to activate the photoinitiators, as needed. Examples 1-5 illustrate representative formulations for indicator coat 54 which formulations are susceptible to two stage curing. It is presently contemplated that these formulations and transparent coat layer could be applied to the button area 24 of a closure 10 at a closure manufacturer's site. Example 1 10 parts by weight of a UV curable diacrylate bisphenol A epoxy such as Ebercryl 3700 supplied by Radcure is heated to about 50°C. A photo initiator (.4 parts by weight) such as Irgacure 184 supplied by Ciba Geigy, fumed silica (.5 parts by weight) which acts as a suspension agent and opaqifier and an orange fluorescent dye (.005 parts by weight) such as Marigold Orange supplied by Day Glo are added. The composition is mixed sufficiently to obtain a homogenous mixture of all the components. A cowels mixer can be used to increase the speed and efficiency of the mixing. 50 to 100 mg of the material is applied to the center of an up button of an approximate, 50.8mm (two inch) diameter non-sealed closure. The button portion of the closure would already have a black colored background, base coating and bonding/release layer aplied to the button portion of the closure. The material is then spread to an appropriate shape and size such as a disk shape with a diameter of about (19.05mm (3/4 of an inch). The material can be spread in any number of ways to achieve the desired result. One method of spreading is to place the cap on a rotating chuck and use a flat ended spatula to apply and spread the material on the cap. Another method of application is to use an apparatus comprising a motorized rotating chuck into which the cap is secured, a doctor blade attached to one end of a stylus arm and profile bar. A cap can be secured into the chuck and the material to be spread can be applied to the center of the button area. The apparatus motor is started and the doctor blade is brought into contact with the material. The stylus end of the stylus arm is traced over the profile bar which determines the movements of the doctor blade across the cap. After the material is applied to the button area of the cap, it can be partially cured to a non-tacky but flexible solid by exposing it to a light dose of UV radiation and an overcoat layer can be applied. After the cap is applied to the container and the button is drawn down, the indicator coat can be fully cured to a very stiff cross-linked polymer upon exposure to higher doses of UV radiation. When the UV cured indicator coat is in intimate contact with the black backgrounded base coat the color change system when viewed through the indicator coat appears dark green. Upon the button up-flip and activation of the tamper evident coating system, the color change system when viewed through the indicator coat appears orange due to the separation of the indicator coat from the base coat. Example 2 Ebecryl 3700 (7.0 parts by weight)) is heated to about 50°C. An opaqifier such as zinc oxide (2.0 parts by weight) and colorants such as Marigold Orange fluorescent dye (.3 parts by weight) and Mobay yellow fluorescent dye (0.3 parts by weight) are then added. The formulation is mixed with sufficient shearing action to provide a homogenous mixture of all of the components. This mixture is made in order to effectively disperse the dyes and fillers into the indicator formulation in the correct amounts. The main indicator coating can then be formulated by heating Ebecryl 3700 (100 parts by weight) to about 50°C. and then adding the foregoing premix (.1 part by weight), fumed silica (.5 parts by weight) and .1 part by weight of a long wave length photo initiator such as Lucerin TPO supplied by BASF. The resulting material can be applied to a button closure having a black colored background and a base coat and cured in accordance with the methods set forth in Example 1 above. When the UV cured indicator coat is in intimate contact with the black backgrounded base coat the color change system when viewed through the indicator coat appears dark green. Upon activation of the color change system the color change system when viewed through the indicator coat appears orange/yellow due to separation of the indicator coat from the base coat. Example 3 100 parts by weight of a phenyl based epoxy novolac such as Tactix 785 supplied by Dow Co. is heated to the melt state. One part of a cationic photo initiator such as FX-512 supplied by 3M is then added and the components are mixed. The material is allowed to cool and is then crushed into a granular form. 50 to 100 milligrams of the material is applied to the center of the up button of a non-sealed cap. The button would have a black backgrounded base coat in place. The cap is then heated, on a hot plate or with an IR lamp, until the material goes to the melt state. The melted material is then spread to a diameter of about 19.05mm (3/4 of an inch) with a string rod or a spatula. Upon cooling, the material solidifies. Because the material is solid in its uncured state it is not necessary to go through the precure process of Examples 1 and 2 above. Although thermoplastic phenol formaldehyde type resins typically are cured with cross-linking agents such as amines and anhydrides and heat, this formulation can be cured for the present application by exposure to UV energy. When this material is UV cured it turns red in color. Accordingly, after the closure containing the color change system of the present invention incorporating the formulation of Example 3 is applied to the container and a vacuum is drawn the indicator coat can be cured by exposure to UV radiation. When the UV cured indicator coat is in intimate contact with the black colored base coat the color change system when viewed through the indicator coat appears dark green. Upon button up-flip and activation of the tamper evident coating system, the color change system when viewed through the indicator coat appears red due to the separation of the indicator coat from the base coat. Example 4 A photo initiator and colorant premix is prepared of Darocur 4265 (1.96 parts by weight) photo initiator supplied by EM Industries, Mobay yellow 10 GN (1.3 parts by weight) yellow fluorescent dye supplied by Mobay and Pylachrome pink (0.043 parts by weight) pink fluorescent dye supplied by Pylam Corp. The main indicator coating is prepared by adding Ebecryl 220 (141 parts by weight) UV curable hexafunctional urethane acrylate to a 113.4g (four ounce) glass jar. Then a fluoro aliphatic ester surface active agent, surfactant (.214 parts by weight) used to provide good wetting characteristics of the uncured system to the cap such as FC430 supplied by 3M, white pigment such as titanium dioxide (.214 parts by weight) used to provide opacity, the foregoing premix (1.430 parts by weight) and about 2.4 parts by weight of fumed silica such as Cab-O-Sil supplied by Cabot Corporation are added. The mixture is stirred gently with a spatula to entrap the silica. An additional amount of 2.4 parts by weight fumed silica is added and the mixture is vigorously stirred with a cowels blade mixture or otherwise appropriately blended such as by a three roll mill. The resulting material can be applied to a button closure having a black backgrounded base coat in accordance with the methods set forth in Example 1 above. The indicator coat can then be precured by exposure to UV radiation. For example, a Suncure Photocure 2785 Lab UV curing unit housing two 304.8mm (12 inch) (7.87 watts/mm (200 watts/inch)) medium pressure mercury vapor lamps can be used to cure the indicator coat. The indicator coat can be precured by exposure to approximately 0.029 Joules/cm 2 as measured in the wavelength range between about 320 to 390 nm (1 x 150 ft/min at full power on the Suncure unit). An overcoat layer can be applied over the precured indicator coat. For instance, an acrylated urethane overcoat can be prepared using an aliphatic urethane diacrylate such as Photomer 6060 supplied by Henkel. The acrylated urethane is placed in a 113.4g (four ounce) glass jar and heated on a hot plate for approximately 7 minutes at about 200°C. at which time it should be fluid enough to stir with a glass stirring rod. About 10 parts by weight isobornylacrylate and about 2.5 parts by weight N vinylpyrrolidone can be sequentially added to lower the viscosity, improve elongation, improve hardness and increase the curing speed of formulation. About 1 parts by weight of a photo initiator such as Irgacure 184 is added and the components are mixed well. Additional additives such as surfactants can be added to provide other characteristics such as wetting and scruff resistance to the overcoat layer. For instance, about .2 parts by weight of surfactants can be included in the above overcoat formulation to provide wetting and scruff resistance to the overcoat. The overcoat can be applied to the closure such as by applying it in a manner similar to that used to apply the indicator coat to the closure or in any number of other ways to achieve the desired result. The overcoat can then be cured by exposure to approximately 0.026 Joules/cm 2 as measured in the wavelength range between about 320 to 390 nm (1 x 100 ft/min at low power on the Suncure unit). After the closure has been applied to the container and the button is drawn down, the indicator coat can be fully cured to a very stiff-cross-linked polymer by further exposure to approximately 0.518 Joules/cm 2 as measured in the wavelength range between about 320 to 390 nm (5 x 50 ft/min at full power on the Suncure unit). When the UV cured indicator coat is in intimate contact with the black backgrounded base coat the color change system when viewed through the indicator coat appears green. Upon activation of the color change system, the color change system when viewed through the indicator coat appears orange due to separation of the indicator coat from the base coat. Example 5 25 parts by weight of an aromatic diacrylate urethane, PES 198 supplied by Polymer Systems, is heated to 50°C. 25 parts by weight of a bisphenol A epoxy diacrylate such as Henkel 3016 is added to the heated aromatic diacrylate urethane and 50 parts by weight of a hexafunctional aromatic urethane acrylate used to increase cross-linked density such as Henkel 6022 is added. 2 parts by weight of a photo initiator such as Darocur 1173 supplied by EM Industries and 2.5 parts by weight of calcium carbonate which is used to provide opacity are added. A desired amount of a colorant preferably a light colored fluorescent dye can also be added. The formulation can be applied to a dark backgrounded base coat button closure and cured in accordance with the procedures set forth in Example 4 above. When the UV indicator coat is in intimate contact with the black backgrounded base coat the color change system when viewed through the indicator coat will have a first color. Upon activation of the color change system, the color change system when viewed through the indicator coat will have a second color different from the first color due to separation of the indicator coat from the base coat. It will be appreciated that although the formulations set forth in Examples 1-5, above, have been described in the context of two stage curing systems that such formulations can also be used in a single stage curable system such as by application to a base coating 34 on a button closure 10 which has already been applied to a container and drawn down by a vacuum therein. In such a single stage application, the indicator coat 36 would be subjected to sufficient curing means, such as chemical curing means, thermal curing means or radiation such as UV radiation curing means, to effect the desired amount of curing of the indicator coat 36 resin. Examples 6 and 7 illustrate further representative formulations for indicator coat 36 which formulations are susceptible to single stage curing. It is presently contemplated that these formulations could be applied to the button area 24 of a closure 10 at the packaging site after the closure 10 has been applied to a container and the container is sealed and the button 24 has been drawn to its down position. The button 24 would have a dark background and base coat 34 such as an epoxy ester varnish base coat in place. Although only one preferred embodiment of the invention have been specifically illustrated and described herein, it will be understood that minor variations may be made in the color change system of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.

Claims: A container including a container body and a removable closure (10) sealingly applied to said container body, said closure (10) including a flexible end panel portion (12) having formed therein a sealing state indicating area (24) which can flex from a seal indicating position to a non-seal indicating position due to the release of energy stored within said end panel (12), said sealing state indicating area (24) carrying an irreversible tamper indicating color change system (32) comprising an effectively dark coloured base layer (52), and a translucent light coloured indicator layer (54), characterised in that the container includes a photo degradable bonding/release layer (56) interposed between said base layer (52) and said indicator layer (54), said photo degradable bonding/release layer having been partially degraded after application so as to weaken the attachment of said bonding/release layer to said base layer and said indicator layer, whereby when said flexible end panel (12) is in a seal indicating position said degradable bonding/release layer maintains said base layer (52) and said indicator layer (54) in effective intimate contact with each other so that when viewed through said indicator layer (54) said color change system has an effective first color, and when said flexible end panel (12) flexes to its non-seal indicating position, said bonding/release layer is broken such that said indicator layer (54) separates from said base layer (52) and said color change system when viewed through said indicator layer (54) has a second color different from said first color. A container according to claim 1 wherein said bonding/release layer is a photodegradable polymer. A container according to claim 2 wherein said photodegradable polymer is a photodegradable polystyrene. A container according to any preceding claim wherein said indicator layer (54) comprises a coloured translucent plastic disc. A container according to any preceding claim wherein said color change system (32) further comprises a transparent overcoat (62) which prevents said indicator layer (54) from falling off said closure when said indicator layer (54) separates from said base layer (52). A container according to claim 5 wherein said color change system (32) further comprises means between said indicator layer (54) and said overcoat (62) to inhibit bonding between said indicator layer (54) and said overcoat (62). A container according to claim 6 wherein said means comprising a surfactant. A container according to any preceding claim further comprising means for creating a stress center to facilitate separation of said indicator layer (54) from said base layer (52) when said flexible end panel flexes to its non-seal indicating position.

Inventors: BIALKA DANIEL P, HEKEL IHAB, ILER HOWARD DARRELL, KISS BRADLEY C, BIALKA, DANIEL P., HEKEL, IHAB, ILER, HOWARD DARRELL, KISS, BRADLEY C.
Applicants: CONTINENTAL WHITE CAP INC, CONTINENTAL WHITE CAP, INC.
Application year: 1993
Main classification: B65D55
IPC codes: B65D55, B65D41, B65D79