US3896965A - Tamper indicator tape - Google Patents
Tamper indicator tape Download PDFInfo
- Publication number
- US3896965A US3896965A US397797A US39779773A US3896965A US 3896965 A US3896965 A US 3896965A US 397797 A US397797 A US 397797A US 39779773 A US39779773 A US 39779773A US 3896965 A US3896965 A US 3896965A
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- United States
- Prior art keywords
- closure
- color
- aperture
- indicator layer
- capsules
- Prior art date
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Classifications
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0292—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time tamper indicating labels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D17/00—Rigid or semi-rigid containers specially constructed to be opened by cutting or piercing, or by tearing of frangible members or portions
- B65D17/50—Non-integral frangible members applied to, or inserted in, preformed openings, e.g. tearable strips or plastic plugs
- B65D17/501—Flexible tape or foil-like material
- B65D17/502—Flexible tape or foil-like material applied to the external part of the container wall only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D55/00—Accessories for container closures not otherwise provided for
- B65D55/02—Locking devices; Means for discouraging or indicating unauthorised opening or removal of closure
- B65D55/026—Locking devices; Means for discouraging or indicating unauthorised opening or removal of closure initial opening or unauthorised access being indicated by a visual change using indicators other than tearable means, e.g. change of colour, pattern or opacity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2401/00—Tamper-indicating means
- B65D2401/55—Tamper-indicating means based on a change or a contrast in colour
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2517/00—Containers specially constructed to be opened by cutting, piercing or tearing of wall portions, e.g. preserving cans or tins
- B65D2517/0001—Details
- B65D2517/001—Action for opening container
- B65D2517/0013—Action for opening container pull-out tear panel, e.g. by means of a tear-tab
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2517/00—Containers specially constructed to be opened by cutting, piercing or tearing of wall portions, e.g. preserving cans or tins
- B65D2517/0001—Details
- B65D2517/0058—Other details of container end panel
- B65D2517/0059—General cross-sectional shape of container end panel
- B65D2517/0061—U-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2517/00—Containers specially constructed to be opened by cutting, piercing or tearing of wall portions, e.g. preserving cans or tins
- B65D2517/50—Non-integral frangible members applied to, or inserted in, a preformed opening
- B65D2517/5002—Details of flexible tape or foil-like material
- B65D2517/5024—Material
- B65D2517/5032—Laminated
- B65D2517/5035—Laminated and connected to container by local areas of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2517/00—Containers specially constructed to be opened by cutting, piercing or tearing of wall portions, e.g. preserving cans or tins
- B65D2517/50—Non-integral frangible members applied to, or inserted in, a preformed opening
- B65D2517/5072—Details of hand grip, tear- or lift-tab
- B65D2517/5083—Details of hand grip, tear- or lift-tab with means facilitating initial lifting of tape, e.g. lift or pull-tabs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S206/00—Special receptacle or package
- Y10S206/807—Tamper proof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/916—Fraud or tamper detecting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- ABSTRACT An easy opening, hermetically sealed container with a preformed aperture is covered by a tape closure having on its outer surface an indicator layer which changes color when flexed, thereby indicating whether the closure has been handled or tampered with.
- containers have been hermetically sealed with easily opened tape closures which are affixed over a hole, or aperture, in the container wall by heat sealing or a pressure-sensitive adhesive; see US Pat. No. 3,389,827.
- the closure has one free end which is easily gripped by fingers and pulled so as to separate it from the can.
- the contents e.g. fruit juice, oil, salt, etc. can then be removed via the exposed aperture.
- This closure provides a good, effective seal and has gained wide acceptance for sealing open cans. It is possible, however, to carefully break the seal, remove or adulterate the contents of the can, and then replace the tape closure, leaving no readily visible traces of the tampering.
- a tape closure having a tamper indicator system which changes color when an attempt has been made to remove it with the aid of an organic solvents is disclosed in US. Pat. No. 3,680,236.
- This indicator incorporates a layer containing a dye which dissolves and stains the backing when it is contacted with an organic solvent such as kerosene or toluene. Such an indicator will not function where the tape closure is removed by purely mechanical means.
- the modified tape closure of this invention has on at least a portion of its exposed face an indicator layer comprising a strong, flexible binder matrix throughout which are dispersed a solid color-forming material and capsules filled with a liquid which includes a dye precursor reactable with the color-forming material. If the dye precursor is not itself a liquid, it can be dissolved in a suitable solvent. When the closure is flexed by force applied to the free end of the closure, the capsules rupture and the colorforming material reacts with the dye precursor to form a colored dye, indicating the can closure has been tampered with. At least a portion of the indicator layer lies in the area intermediate the free end of the closure and the near edge of the aperture so that an attempt to remove the closure causes a color change in the indicator strip before any portion of the aperture is exposed.
- the indicator layer can either be formed as a strip of tape which is attached to the back of a conventional tape closure or as a sheet of material from which complete can closures are cut. Either embodiment allows the production of a convolutely wound roll of sheet material which can be subsequently cut into tape closures of any desired size or configuration.
- An indicator strip can be formed from a polymeric film backing material, e.g., biaxially oriented polyethylene terephthalate film, normally having a thickness of about 1 to 3 mils.
- a polymeric film backing material e.g., biaxially oriented polyethylene terephthalate film, normally having a thickness of about 1 to 3 mils.
- suitable backings include films of cellulose acetate, aluminum vapor-coated polyester, cellophane, polyvinyl chloride, metal foils, polyurethane-saturated flat stock paper, etc.
- the backing should be chosen so it is adhesive receptive but is not degraded or otherwise adversely affected by the binder or its solvents.
- a presently preferred backing material is biaxially oriented polyethylene terephthalate film.
- the indicator strip is secured to the tape closure by an adhesive, such as an acrylate, rubber-resin or other adhesive commonly used in the pressure-sensitive tape art. Hot melt or solvent activated adhesives could be used but are more difficult to apply and pressuresensitive adhesives are preferred because of their ease of application.
- the adhesive should bond the backing to the tape closure so that the indicator strip will not delaminate from the tape closure when the tape closure is flexed and any attempt to pull the indicator strip off the tape closure will activate the indicator strip.
- an indicator coating comprising a combination of binder resin, reactant materials, and perhaps fillers.
- the reactant materials which comprise (l) a liquid consisting essen tially of a dye precursor and (2) a color-forming substance, will react to form a dye.
- the liquid dye precursor is encapsulated and separated from the coreactant to prevent premature color development.
- the color-forming substance is a finely dispersed solid material; however, it could also be an encapsulated liquid.
- the binder resin should have a high enough tensile or Youngs modulus that the force exerted to flex the closure tab upon opening will rupture the enclosed capsules. Suitable binder resins can be selected from the acrylics, polystyrene, polyvinylchloride, polyvinylbutyral, polycarbonate, etc.
- the binder should have a minimum Youngs modulus, measured at 2% elongation, of 125,000 psi. Binders having a significantly lower Youngs modulus will deform when the tape closure is flexed, so that the capsules will not rupture to release the liquid, and hence satisfactory color change does not take place.
- the binder resin is preferably pale or water white, but in any case, it should not have a distinct color which would block or otherwise obscure the color of the dye formed during flexing of the closures.
- the resin chosen should also be compatible with the backing on which it is coated.
- a suitable color forming combination is nickel rosinate and dithiooxamide derivatives, both of which are initially colorless but which react to form a deep purple dye.
- a further example is triphenyl methane leuco and acidic clays, which react to form a blue to purple color.
- leuco methyl violet which reacts to form brown. The leuco form of Malachite Green reacts with tannic acid to form a deep green.
- Suitable liquid-containing microcapsules may be produced by dispersing the liquid dye precursor as finely divided droplets in an aqueous, water-soluble ureaformaldehyde precondensate solution, and acidcatalyzing the precondensate to form ureaformaldehyde polymer, around the dispersed droplets.
- a process for making encapsulated liquid materials can be found in US. Pat. Nos. 3,516,846 and 3,516,941, the disclosures of which are incorporated herein by reference.
- the capsules containing the liquid reactant will generally represent about one-third to one-half by volume of the indicator layer. Above one-half by volume the capsules represent such a large portion of the indicator that it simply falls apart when the closure is flexed. As the percentage of capsules in the indicator layer is decreased substantially below about one-third by volume, the intensity of the color formed by flexing the closures decreases, and removing the tape closure at shallow angles, e.g., about 45 to 60, does not produce a deep color change. Thus, these closures would be subject to careful tampering and are not preferred for containers with food items. Such closures could be useful in less stringent applications, such as sealing oil containers, etc.
- a pigment such as titanium dioxide, may be added to the binder to provide a contrasting background and enhance the visibility of color changes, increasing the tamper indicators sensitivity.
- the indicator coating will generally be about 0.5 to mils in thickness, preferably about 1 to 3 mils. Coating thicknesses below about 1 mil develop less color than heavier coatings when the closure is pulled off at a shallow angle. Coatings of 3 to 5 mils and greater are more difficult to apply and have a tendency to crack when sharply flexed, thereby reducing the intensity of the color change.
- the indicator layer may be either a continuous film or in the form of a pattern, such as squares or dots.
- the indicator can also be applied in the shape of a word such as opened, which would become highly colored when the closure is flexed and thereby emphasize that the seal had been tampered with.
- FIG. 1 is a top plan view of a can lid having an aperture covered by a tape closure of this invention
- FIG. 2 is a cross-sectional view of FIG. 1 taken along the section line 2-2, looking in the direction of the arrows;
- FIG. 3 is an enlarged cross-sectional view of another type of tape closure made in accordance with the invention.
- FIG. 4 is a perspective view of a roll of tape suitable for making can closures of this invention.
- can top is provided with aperture 12, tape closure 14 overlying can top 10 and sealing aperture 12.
- C10- sure 14 comprises film backing sheet 26, adhesive being applied over the lower surface thereof and serving to bond closure 14, to can top 10.
- adhesive 20 is covered by a small piece of film 19, thereby forming grip tab 18 to aid inremoval.
- film backing layer 26 On the upper surface of film backing layer 26 is a layer of binder material 23, throughout which are dispersed capsules 24 filled with liquid dye precursor and finely divided particles of material capable of reacting with the dye precursor to form a dye.
- FIG.. 3 shows another embodiment of this invention, where the indicator layer is incorporated as part of a separate tape construction 21.
- Layer 22, comprising liquid-containing capsules 24 in binder 23 is coated on and bonded to film substrate 27 to form a laminate.
- the resulting laminate is then adhered to the top surface of film 26 by adhesive layer 28.
- a roll 30 of material suitable for forming the can closure of this invention is shown in FIG. 4.
- a film 26 suitable for forming can closures has a strip of indicator material 16 longitudinally adhered to the film.
- Can closures having the desired configuration can be die-cut from roll 30 and the resulting closure mounted on a can top as shown in FIG. 1 or 2.
- nickel rosinate 13.2 parts isophthalic-terephthalic acid/ethylene glycol copolyester resin having a ring and ball softening point of 155C. (Vitel PE-200, available from Goodyear Chemical Co.), diluted to 40% solids with a 1:2 toluol-methyl ethyl ketone solvent;
- a pressure sensitive adhesive was made by milling 100 parts Kraton 1101 block copolymer (an ABA block copolymer where A is 15,000 molecular weight polystyrene and B is 30,000 molecular weight polybutadiene) and parts Hercules S1010, a B-terpene.
- the blend was diluted with toluene to 40% solids and knife coated on the film surface opposite the dry indicator layer.
- the film was dried at 65C. for 20 minutes to evaporate the toluene, leaving 15 grains of adhesive per 24 square inches.
- the coated film was adhesively bonded to the upper surface of a can closure similar to that disclosed in Example 11 of US. Pat. No. 3,389,827.
- the indicator layer turned deep purple when the closure was removed from a can top even at shallow angles.
- EXAMPLE 2 A closure like that of Example 1 was made using as the coating mixture 18 parts of the capsules described in Example 1, 9 parts nickel rosinate, 13.2 parts 40% solids Vitel PE20O in a 1:2 toluene:methyl ethyl ketone solvent, and 21.6 parts of methyl ethyl ketone.
- the resulting indicator closures give a slightly deeper purple color than those of Example 1 when the closures were removed from can tops at shallow angles of about 45.
- Example 3 A closure like that of Example 1 was made using a coating comprising 18 parts capsules of Example 1 18 parts nickel rosinate parts 35% solids Vitel PE-200 in cyclohexanone;
- EXAMPLE 4 A family of blends of Vitel PEZOO and Vitel PE207 (the latter being an isophthalic-terephthalic acid/ethylene glycol copolymer having a ring and ball softening point of 127C.), each weighing 200 grams, were prepared by milling on a two roll rubber mill at about 310F. for about 10 minutes and allowed to cool. The blends were hot pressed at 375F. between two sheets of release paper, using a force of 10,000 pounds, to form sheets about 50 to 65 mils thick.
- Test pieces conforming to ASTM Test Standard D1708-66, were stamped from the sheets using a standard die.
- the test pieces were dumbbell-shaped, approximately 1.5 inches long 0.625 inch wide in their greatest dimension, with a reduced center section 0.876 inch long and 0.187 inch wide.
- Samples h-k were brittle and heated with a warm air gun until the polymer started to soften to facilitate stamping.
- the die-cut pieces were stress-relieved in a warm air oven at 150F., for a sufficient time to insure that no residual stress remained from stamping and then conditioned for 24 hours at 72F. and 50% relative humidity.
- the resulting closures were mounted on can lids and removed at three different angles. First, the closures were pulled away at a shallow angle, where the angle between the adhesivecoated surface of the tape closure and the can lid was about 4560. Second, they were pulled vertically away from the can top at a removal angle of about 90. Third, the closures were doubled back upon themselves and pulled away at a removal angle of about 180.
- Closures made with binder compositions h-k produced a deep purple color change, even when removed 1 at shallow angles.
- closures made with binder compositions a-g did not give an acceptable color change when removed even at angles of 90-180.
- Example 1 was repeated, employing the same amounts of capsules and nickel rosinate but varying the binder system.
- Binders used were:
- VYNS polyvinylchloride available from Union Carbide
- Tape closures made with binders (a) and (c) produced a faint lavender when pulled from can tops at a shallow angle, the depth and amount of color increasing when the closure is pulled off at 90 or more.
- a hermetically sealed container which encloses pourable material within a rigid wall having a preformed aperture therein, said aperture being covered and said container being hermetically sealed by a closure comprising a sheet material removably adhered directly to the portion of said wall which surrounds said aperture, said closure having a free end not attached to said wall, said closure being capable of being grasped by said free end and pulled back on itself without rupture to expose the underlying aperture and permit removal of the pourable material, the improvement which comprises:
- an indicator layer comprising a strong, flexible binder matrix having a Youngs modulus at 2% elongation of at least about 125,000 pounds per square inch containing, dispersed throughout, a solid color-forming substance and capsules containing a liquid dye precursor reactable with said color-forming substance, at least a portion of said indicator layer being intermediate said free end and the nearer edge of said aperture,
Abstract
An easy opening, hermetically sealed container with a preformed aperture is covered by a tape closure having on its outer surface an indicator layer which changes color when flexed, thereby indicating whether the closure has been handled or tampered with.
Description
United States Cornell atent 1 [4 1 July 29, 1975 1 TAMPER INDICATOR TAPE [75] Inventor: Lew Wallace Cornell, Mound, Minn.
[73] Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.
22 Filed: Sept. 17, 1973 21 Appl. No.: 397,797
[52] U.S. Cl. 220/359; 117/1; 161/DIG. 1; 161/162; 161/167; 161/406; 206/807; 283/8 [51] Int. Cl. G09f 3/03 [58] Field of Search 161/D1G. 1, 5, 167, 231,
161/406, 214, 225, 162; 206/459, 807, 813; 220/DIG. 16, 214, 359; 283/8 R, 8 B, 21; 117/1; 215/230 [56] References Cited UNITED STATES PATENTS 2,980,569 4/1961 Wening 161/225 X 3,389,827 6/1968 Abere et a1. 220/53 3,411,976 11/1968 Heliker et a1. 161/5 3,423,280 1/1969 Wiener 161/214 X 3,516,846 6/1970 Matson 252/316 X 3,516,941 6/1970 Matson 252/316 3,680,236 8/1972 Deal et a1. 40/22 Primary Examiner-Harold Afisher Assistant Examiner-Henry F. Epstein Attorney, Agent, or FirmAlexander, Sell, Steldt & DeLal-lunt [57] ABSTRACT An easy opening, hermetically sealed container with a preformed aperture is covered by a tape closure having on its outer surface an indicator layer which changes color when flexed, thereby indicating whether the closure has been handled or tampered with.
7 Claims, 3 Drawing Figures PATENTEB JUL 2 9 I975 SHEET SHEET PATENTED JUL 2 91975 TAMPER INDICATOR TAPE BACKGROUND OF THE INVENTION This invention relates to an improved tape container closure.
In recent years containers have been hermetically sealed with easily opened tape closures which are affixed over a hole, or aperture, in the container wall by heat sealing or a pressure-sensitive adhesive; see US Pat. No. 3,389,827. The closure has one free end which is easily gripped by fingers and pulled so as to separate it from the can. The contents, e.g. fruit juice, oil, salt, etc. can then be removed via the exposed aperture.
This closure provides a good, effective seal and has gained wide acceptance for sealing open cans. It is possible, however, to carefully break the seal, remove or adulterate the contents of the can, and then replace the tape closure, leaving no readily visible traces of the tampering.
A tape closure having a tamper indicator system which changes color when an attempt has been made to remove it with the aid of an organic solvents, is disclosed in US. Pat. No. 3,680,236. This indicator incorporates a layer containing a dye which dissolves and stains the backing when it is contacted with an organic solvent such as kerosene or toluene. Such an indicator will not function where the tape closure is removed by purely mechanical means.
BRIEF SUMMARY OF THE INVENTION This invention comprises a modification of tape closures such as those described in aforementioned US. Pat. No. 3,389,827, the disclosure of which is incorporated herein by reference.
The modified tape closure of this invention has on at least a portion of its exposed face an indicator layer comprising a strong, flexible binder matrix throughout which are dispersed a solid color-forming material and capsules filled with a liquid which includes a dye precursor reactable with the color-forming material. If the dye precursor is not itself a liquid, it can be dissolved in a suitable solvent. When the closure is flexed by force applied to the free end of the closure, the capsules rupture and the colorforming material reacts with the dye precursor to form a colored dye, indicating the can closure has been tampered with. At least a portion of the indicator layer lies in the area intermediate the free end of the closure and the near edge of the aperture so that an attempt to remove the closure causes a color change in the indicator strip before any portion of the aperture is exposed.
The indicator layer can either be formed as a strip of tape which is attached to the back of a conventional tape closure or as a sheet of material from which complete can closures are cut. Either embodiment allows the production of a convolutely wound roll of sheet material which can be subsequently cut into tape closures of any desired size or configuration.
An indicator strip can be formed from a polymeric film backing material, e.g., biaxially oriented polyethylene terephthalate film, normally having a thickness of about 1 to 3 mils. Other suitable backings include films of cellulose acetate, aluminum vapor-coated polyester, cellophane, polyvinyl chloride, metal foils, polyurethane-saturated flat stock paper, etc. The backing should be chosen so it is adhesive receptive but is not degraded or otherwise adversely affected by the binder or its solvents. A presently preferred backing material is biaxially oriented polyethylene terephthalate film.
The indicator strip is secured to the tape closure by an adhesive, such as an acrylate, rubber-resin or other adhesive commonly used in the pressure-sensitive tape art. Hot melt or solvent activated adhesives could be used but are more difficult to apply and pressuresensitive adhesives are preferred because of their ease of application. The adhesive should bond the backing to the tape closure so that the indicator strip will not delaminate from the tape closure when the tape closure is flexed and any attempt to pull the indicator strip off the tape closure will activate the indicator strip.
On the exposed side of the backing, opposite the adhesive, is an indicator coating comprising a combination of binder resin, reactant materials, and perhaps fillers. if allowed to contact eaclh other the reactant materials, which comprise (l) a liquid consisting essen tially of a dye precursor and (2) a color-forming substance, will react to form a dye. The liquid dye precursor, however, is encapsulated and separated from the coreactant to prevent premature color development. Normally the color-forming substance is a finely dispersed solid material; however, it could also be an encapsulated liquid. The binder resin should have a high enough tensile or Youngs modulus that the force exerted to flex the closure tab upon opening will rupture the enclosed capsules. Suitable binder resins can be selected from the acrylics, polystyrene, polyvinylchloride, polyvinylbutyral, polycarbonate, etc.
In order to provide a system which will insure rupture of the capsules, it has been determined empirically that the binder should have a minimum Youngs modulus, measured at 2% elongation, of 125,000 psi. Binders having a significantly lower Youngs modulus will deform when the tape closure is flexed, so that the capsules will not rupture to release the liquid, and hence satisfactory color change does not take place.
The binder resin is preferably pale or water white, but in any case, it should not have a distinct color which would block or otherwise obscure the color of the dye formed during flexing of the closures. The resin chosen should also be compatible with the backing on which it is coated.
When the closure is flexed, the capsules rupture, the encapsulated liquid is released, and the co-reactants form a dye. One example of a suitable color forming combination is nickel rosinate and dithiooxamide derivatives, both of which are initially colorless but which react to form a deep purple dye. A further example is triphenyl methane leuco and acidic clays, which react to form a blue to purple color. Also useful is leuco methyl violet, which reacts to form brown. The leuco form of Malachite Green reacts with tannic acid to form a deep green.
Suitable liquid-containing microcapsules may be produced by dispersing the liquid dye precursor as finely divided droplets in an aqueous, water-soluble ureaformaldehyde precondensate solution, and acidcatalyzing the precondensate to form ureaformaldehyde polymer, around the dispersed droplets. A process for making encapsulated liquid materials can be found in US. Pat. Nos. 3,516,846 and 3,516,941, the disclosures of which are incorporated herein by reference.
The capsules containing the liquid reactant will generally represent about one-third to one-half by volume of the indicator layer. Above one-half by volume the capsules represent such a large portion of the indicator that it simply falls apart when the closure is flexed. As the percentage of capsules in the indicator layer is decreased substantially below about one-third by volume, the intensity of the color formed by flexing the closures decreases, and removing the tape closure at shallow angles, e.g., about 45 to 60, does not produce a deep color change. Thus, these closures would be subject to careful tampering and are not preferred for containers with food items. Such closures could be useful in less stringent applications, such as sealing oil containers, etc.
If desired, a pigment, such as titanium dioxide, may be added to the binder to provide a contrasting background and enhance the visibility of color changes, increasing the tamper indicators sensitivity.
The indicator coating will generally be about 0.5 to mils in thickness, preferably about 1 to 3 mils. Coating thicknesses below about 1 mil develop less color than heavier coatings when the closure is pulled off at a shallow angle. Coatings of 3 to 5 mils and greater are more difficult to apply and have a tendency to crack when sharply flexed, thereby reducing the intensity of the color change.
The indicator layer may be either a continuous film or in the form of a pattern, such as squares or dots. The indicator can also be applied in the shape of a word such as opened, which would become highly colored when the closure is flexed and thereby emphasize that the seal had been tampered with.
BRIEF DESCRIPTION OF THE DRAWINGS A further understanding of the invention may be had by referring to the accompanying drawing in which like numbers refer to like parts in the several views and in which:
FIG. 1 is a top plan view of a can lid having an aperture covered by a tape closure of this invention;
FIG. 2 is a cross-sectional view of FIG. 1 taken along the section line 2-2, looking in the direction of the arrows;
FIG. 3 is an enlarged cross-sectional view of another type of tape closure made in accordance with the invention; and
FIG. 4 is a perspective view of a roll of tape suitable for making can closures of this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings, and initially to FIGS. 1 and 2, can top is provided with aperture 12, tape closure 14 overlying can top 10 and sealing aperture 12. C10- sure 14 comprises film backing sheet 26, adhesive being applied over the lower surface thereof and serving to bond closure 14, to can top 10. At the distal portion of closure 14, adhesive 20 is covered by a small piece of film 19, thereby forming grip tab 18 to aid inremoval.
On the upper surface of film backing layer 26 is a layer of binder material 23, throughout which are dispersed capsules 24 filled with liquid dye precursor and finely divided particles of material capable of reacting with the dye precursor to form a dye.
When tab 18 is gripped and pulled upward to remove closure 14 from top 10, capsules 24 will rupture, thereby releasing their liquid contents, which will react with the solid coreactant to form a dye and thus show that closure 14 has been tampered with. Even if closure 14 is thereafter reapplied to can top 10, the evidence of the prior opening of the seal remains.
FIG.. 3 shows another embodiment of this invention, where the indicator layer is incorporated as part of a separate tape construction 21. Layer 22, comprising liquid-containing capsules 24 in binder 23, is coated on and bonded to film substrate 27 to form a laminate. The resulting laminate is then adhered to the top surface of film 26 by adhesive layer 28.
A roll 30 of material suitable for forming the can closure of this invention is shown in FIG. 4. A film 26 suitable for forming can closures has a strip of indicator material 16 longitudinally adhered to the film. Can closures having the desired configuration can be die-cut from roll 30 and the resulting closure mounted on a can top as shown in FIG. 1 or 2.
The invention is further described with reference to the following examples. All parts are by weight unless otherwise noted.
EXAMPLE 1 A mixture comprising:
9.0 parts of the condensed formaldehyde capsules containing derivatives of dithiooxamide described in US. Pat. No. 3,516,941, Example 18, having a diameter of about 15 microns;
9.0 parts nickel rosinate 13.2 parts isophthalic-terephthalic acid/ethylene glycol copolyester resin having a ring and ball softening point of 155C. (Vitel PE-200, available from Goodyear Chemical Co.), diluted to 40% solids with a 1:2 toluol-methyl ethyl ketone solvent;
13.5 parts methyl ethyl ketone was gently blended, to prevent capsule rupture, to a uniform consistency with an air driven propeller mixer and knife coated at a wet thickness of 3 mils on 1 mil biaxially oriented polyethylene terephthalate film. The coating was dried at 65C. for 20 minutes to form a dry indicator layer between 1 and 2 mils (0.025 0.05 mm.) thick.
A pressure sensitive adhesive was made by milling 100 parts Kraton 1101 block copolymer (an ABA block copolymer where A is 15,000 molecular weight polystyrene and B is 30,000 molecular weight polybutadiene) and parts Hercules S1010, a B-terpene. The blend was diluted with toluene to 40% solids and knife coated on the film surface opposite the dry indicator layer. The film was dried at 65C. for 20 minutes to evaporate the toluene, leaving 15 grains of adhesive per 24 square inches. The coated film was adhesively bonded to the upper surface of a can closure similar to that disclosed in Example 11 of US. Pat. No. 3,389,827. The indicator layer turned deep purple when the closure was removed from a can top even at shallow angles.
EXAMPLE 2 A closure like that of Example 1 was made using as the coating mixture 18 parts of the capsules described in Example 1, 9 parts nickel rosinate, 13.2 parts 40% solids Vitel PE20O in a 1:2 toluene:methyl ethyl ketone solvent, and 21.6 parts of methyl ethyl ketone.
The resulting indicator closures give a slightly deeper purple color than those of Example 1 when the closures were removed from can tops at shallow angles of about 45.
' EXAMPLE 3 A closure like that of Example 1 was made using a coating comprising 18 parts capsules of Example 1 18 parts nickel rosinate parts 35% solids Vitel PE-200 in cyclohexanone;
and
28.8 parts cyclohexanone The resulting indicator closures changed color when removed from can lids. When the closures were removed at 45, the color was light purple, lighter than in previous examples, although still acceptable.
EXAMPLE 4 A family of blends of Vitel PEZOO and Vitel PE207 (the latter being an isophthalic-terephthalic acid/ethylene glycol copolymer having a ring and ball softening point of 127C.), each weighing 200 grams, were prepared by milling on a two roll rubber mill at about 310F. for about 10 minutes and allowed to cool. The blends were hot pressed at 375F. between two sheets of release paper, using a force of 10,000 pounds, to form sheets about 50 to 65 mils thick.
Test pieces, conforming to ASTM Test Standard D1708-66, were stamped from the sheets using a standard die. The test pieces were dumbbell-shaped, approximately 1.5 inches long 0.625 inch wide in their greatest dimension, with a reduced center section 0.876 inch long and 0.187 inch wide. Samples h-k were brittle and heated with a warm air gun until the polymer started to soften to facilitate stamping. The die-cut pieces were stress-relieved in a warm air oven at 150F., for a sufficient time to insure that no residual stress remained from stamping and then conditioned for 24 hours at 72F. and 50% relative humidity.
The samples were mounted in an Instron tensile machine and the jaws separated at a rate of 1 inch/mi nute until break or a 10% elongation was reached, whichever occurred first. The average Youngs moduli of 3 tensile specimens of each blend are given in Table l.
Blends of resins, corresponding to the samples, were made and used in place of the Vitel PEZOO as a binder resin in making tape closures which were otherwise identical to that of Example 1. The resulting closures were mounted on can lids and removed at three different angles. First, the closures were pulled away at a shallow angle, where the angle between the adhesivecoated surface of the tape closure and the can lid was about 4560. Second, they were pulled vertically away from the can top at a removal angle of about 90. Third, the closures were doubled back upon themselves and pulled away at a removal angle of about 180.
'TABLE' [Continued 7 Youngs I %Vitel" PE200 %Vitel" PE207 Mod. at 2% Sample by Weight by Weight Elongation h 7O 30 139,168 i 20 156,667 j 10 r 194,770 k 0 174,496
Closures made with binder compositions h-k produced a deep purple color change, even when removed 1 at shallow angles. On the other hand, closures made with binder compositions a-g did not give an acceptable color change when removed even at angles of 90-180.
Further testing of blends in the composition range lying between samples g and h established that a ration of 2:1 Vitel PE200:PE207 gave a binder composition which gave a light color change when the tape closure was removed at a shallow angle and deeper color at 90-180 removal angles. This blend corresponds to a binder having a Youngs modulus at 2% of about 125,000 psi. Ratios of 3:1 gave a good color change even when removed at shallow angles and have a Youngs modulus at 2% of about 150,000 psi.
EXAMPLE 5 Example 1 was repeated, employing the same amounts of capsules and nickel rosinate but varying the binder system.
Binders used were:
a. 31.5 parts of a 16.8 weight percent solids VYNS (polyvinylchloride available from Union Carbide) resin in methyl ethyl ketone, 6.0 parts MEK, having a Youngs modulus of 280,000 psi;
b. 35.1 parts of 15 weight percent solids polyvinyl butyral in toluol (available as Butvar B76 from Shawinigan Chemicals), 21 parts toluol and 6 parts methyl ethyl ketone, having a Youngs modulus of 227,000 psi; and
c. 23.4 parts of 22.5 weight percent solids polycarbonate in dichloromethane (available as Rowlux from Rowland Products), and 18 parts dichloromethane, having a Youngs modulus of 207,000 ps1.
Tape closures made with binders (a) and (c) produced a faint lavender when pulled from can tops at a shallow angle, the depth and amount of color increasing when the closure is pulled off at 90 or more.
Tape closures made using binder (b) produced a light purple color when removed at 90 and deep color when pulled back upon itself at What is claimed is:
1. In a hermetically sealed container which encloses pourable material within a rigid wall having a preformed aperture therein, said aperture being covered and said container being hermetically sealed by a closure comprising a sheet material removably adhered directly to the portion of said wall which surrounds said aperture, said closure having a free end not attached to said wall, said closure being capable of being grasped by said free end and pulled back on itself without rupture to expose the underlying aperture and permit removal of the pourable material, the improvement which comprises:
on the outer surface of said closure an indicator layer comprising a strong, flexible binder matrix having a Youngs modulus at 2% elongation of at least about 125,000 pounds per square inch containing, dispersed throughout, a solid color-forming substance and capsules containing a liquid dye precursor reactable with said color-forming substance, at least a portion of said indicator layer being intermediate said free end and the nearer edge of said aperture,
whereby, when said closure is flexed by force applied to said free end, said capsules rupture and the color-forming substance and dye precursor react to form a colored dye indicating that said can closure has been at least partially removed.
2. The closure of claim 1, where said color forming solid reactant is nickel rosinate and said liquid color former is a dithiooxamide derivative.
3. The closure of claim 1, where said indicator layer is mounted on a polyester film, said film being secured to the closure.
4. The closure of claim 1 containing titanium dioxide pigment dispersed in the indicator layer.
5. The closure of claim 1 wherein the capsules comprise about one-third to one-half by volume of the binder matrix.
6. The closure of claim 1 wherein said indicator layer is in the form of a printed pattern.
7. The closure of claim 1, wherein said binder is an isophthalic-terephthalic acid/ethylene glycol copolyester resin.
Claims (7)
1. In a hermetically sealed container which encloses pourable material within a rigid wall having a preformed aperture therein, said aperture being covered and said container being hermetically sealed by a closure comprising a sheet material removably adhered directly to the portion of said wall which surrounds said aperture, said closure having a free end not attached to said wall, said closure being capable of being grasped by said free end and pulled back on itself without rupture to expose the underlying aperture and permit removal of the pourable material, the improvement which comprises: on the outer surface of said closure an indicator layer comprising a strong, flexible binder matrix having a Young''s modulus at 2% elongation of at least about 125,000 pounds per square inch containing, dispersed throughout, a solid colorforming substance and capsules containing a liquid dye precursor reactable with said color-forming substance, at least a portion of said indicator layer being intermediate said free end and the nearer edge of said aperture, whereby, when said closure is flexed by force applied to said free end, said capsules rupture and the color-forming substance and dye precursor react to form a colored dye indicating that said can closure has been at least partially removed.
2. The closure of claim 1, where said color forming solid reactant is nickel rosinate and said liquid color former is a dithiooxamide derivative.
3. The closure of claim 1, where said indicator layer is mounted on a polyester film, said film being secured to the closure.
4. The closure of claim 1 containing titanium dioxide pigment dispersed in the indicator layer.
5. The closure of claim 1 wherein the capsules comprise about one-third to one-half by volume of the binder matrix.
6. The closure of claim 1 wherein said indicator layer is in the form of a printed pattern.
7. The closure of claim 1, wherein said binder is an isophthalic-terephthalic acid/ethylene glycol copolyester resin.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US397797A US3896965A (en) | 1973-09-17 | 1973-09-17 | Tamper indicator tape |
US05/545,374 US3935960A (en) | 1973-09-17 | 1975-01-30 | Tamper indicator tape |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US397797A US3896965A (en) | 1973-09-17 | 1973-09-17 | Tamper indicator tape |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/545,374 Division US3935960A (en) | 1973-09-17 | 1975-01-30 | Tamper indicator tape |
Publications (1)
Publication Number | Publication Date |
---|---|
US3896965A true US3896965A (en) | 1975-07-29 |
Family
ID=23572657
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US397797A Expired - Lifetime US3896965A (en) | 1973-09-17 | 1973-09-17 | Tamper indicator tape |
Country Status (1)
Country | Link |
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US (1) | US3896965A (en) |
Cited By (41)
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---|---|---|---|---|
US4009892A (en) * | 1975-02-03 | 1977-03-01 | Nickerson Iii Eugene W | Method and product for preventing fraud in document identification |
EP0105971A2 (en) * | 1982-10-18 | 1984-04-25 | Randall Alan Newkirk | Receptacle tampering sensor and indicator and method therefor |
US4454956A (en) * | 1983-05-16 | 1984-06-19 | Minnesota Mining & Manufacturing Company | Tamper indicating composite tape closure |
EP0111900A2 (en) * | 1982-12-21 | 1984-06-27 | Milton Schonberger | Tamper visible indicator for container lid |
WO1984003270A1 (en) * | 1983-02-18 | 1984-08-30 | Tri Tech Syst | Tamper evident closures and packages |
US4505399A (en) * | 1984-06-21 | 1985-03-19 | Weiner Robert C | Tamper-indicating device and method |
US4519515A (en) * | 1982-12-21 | 1985-05-28 | Milton Schonberger | Disc for indicator for tamper-evident lid |
US4715528A (en) * | 1985-09-20 | 1987-12-29 | Tetra Pak International Ab | Reclosable opening arrangement on a packing container |
US4720423A (en) * | 1986-08-25 | 1988-01-19 | Minnesota Mining And Manufacturing Company | Package opening system |
US4781323A (en) * | 1985-08-27 | 1988-11-01 | Minnesota Mining And Manufacturing Company | Reclosable closure assembly for container |
US4865198A (en) * | 1988-02-01 | 1989-09-12 | R. J. Reynolds Tobacco Company | Overwrapped package with tamper indicating means |
US4874096A (en) * | 1987-07-02 | 1989-10-17 | Sales S.P.A. | Sealed packet with an adhesive strip for opening and reclosing |
US4905851A (en) * | 1983-02-18 | 1990-03-06 | Tri-Tech Systems International, Inc. | Tamper evident closures and packages with color changing means and separable portions of the closures and method of forming the same |
US4911302A (en) * | 1988-02-01 | 1990-03-27 | R. J. Reynolds Tobacco Company | Method for imprinting overwrapped packages |
US4986429A (en) * | 1989-06-12 | 1991-01-22 | Singleton Jr Robert | Color indicating tamper-proof seal |
US5020831A (en) * | 1988-12-23 | 1991-06-04 | Arysearch Arylan Ag | Imprinted product with tamperproof seal method of producing product |
WO1991019649A1 (en) * | 1990-06-20 | 1991-12-26 | Alcan International Limited | Color change devices activatable by bending |
USRE33893E (en) * | 1985-08-27 | 1992-04-21 | Minnesota Mining And Manufacturing Company | Reclosable closure assembly for container |
US5153042A (en) * | 1989-05-16 | 1992-10-06 | Minnesota Mining And Manufacturing Company | Tamper-indicating labelstock |
US5152412A (en) * | 1990-07-18 | 1992-10-06 | Continental White Cap, Inc. | Tamper evident closure using microcapsules |
US5219194A (en) * | 1992-02-28 | 1993-06-15 | Viking Corporation | Security seal |
US5234732A (en) * | 1991-03-18 | 1993-08-10 | Philip Morris Inc. | Tamper-indicating wrappers |
US5312680A (en) * | 1991-02-25 | 1994-05-17 | Carolyn N Simpson | Tamper-revealing sealing device for packaged documents |
US5325721A (en) * | 1993-02-17 | 1994-07-05 | Minnesota Mining And Manufacturing Company | System for indicating exposure to preselected temperatures or tampering |
GB2280402A (en) * | 1993-07-19 | 1995-02-01 | Roger William Middleto Bromley | Bleeding tape |
WO1995013229A1 (en) * | 1993-11-10 | 1995-05-18 | Carnaudmetalbox Plc | Closures for containers |
US5631068A (en) * | 1994-08-02 | 1997-05-20 | Trigon Packaging Corporation | Self-containing tamper evident tape and label |
US6531528B1 (en) * | 1999-05-05 | 2003-03-11 | Dap Products Inc. | Ready to use spackle/repair product containing dryness indicator |
US6609865B2 (en) | 2001-12-24 | 2003-08-26 | Ipex Inc. | Color pressure-sensitive fastener |
US20030236165A1 (en) * | 2002-06-25 | 2003-12-25 | Appleton Papers Inc. | Product authentication |
WO2004035400A2 (en) | 2002-10-18 | 2004-04-29 | Alcan International Limited | Containers with peelable closures that change appearance upon bending |
US20040150221A1 (en) * | 2003-01-30 | 2004-08-05 | Brady Worldwide, Inc. | Tamper evident seal |
US20060054526A1 (en) * | 2004-09-13 | 2006-03-16 | Jennifer Dean | Medical article and method of making and using the same |
US20090093063A1 (en) * | 2007-09-07 | 2009-04-09 | Anslyn Eric V | Color Changing and Coverage Indicating Hand Sanitizer |
US20100224630A1 (en) * | 2009-03-06 | 2010-09-09 | Petlak Frank A | Tamper Evident Container With Pull Tab |
US7913870B2 (en) | 2005-05-10 | 2011-03-29 | Pactiv Corporation | Tamper evident container |
US20150004706A1 (en) * | 2013-06-26 | 2015-01-01 | Mridula Nair | Reactive indicator compositions and articles containing same |
US20150004707A1 (en) * | 2013-06-26 | 2015-01-01 | Mridula Nair | Methods for using indicator compositions |
CN106488875A (en) * | 2014-04-15 | 2017-03-08 | 株式会社细川洋行 | Container |
US20180322812A1 (en) * | 2015-02-24 | 2018-11-08 | Validation Security Technology Identification S De Rl De Cv | Smart label system |
US11124332B2 (en) * | 2018-07-31 | 2021-09-21 | Ynb Supply (Asia) Corporation | Ring-peel-seal liner |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4009892A (en) * | 1975-02-03 | 1977-03-01 | Nickerson Iii Eugene W | Method and product for preventing fraud in document identification |
EP0105971A3 (en) * | 1982-10-18 | 1985-07-31 | Randall Alan Newkirk | Receptacle tampering sensor and indicator and method therefor |
EP0105971A2 (en) * | 1982-10-18 | 1984-04-25 | Randall Alan Newkirk | Receptacle tampering sensor and indicator and method therefor |
EP0111900A2 (en) * | 1982-12-21 | 1984-06-27 | Milton Schonberger | Tamper visible indicator for container lid |
US4480760A (en) * | 1982-12-21 | 1984-11-06 | Milton Schonberger | Tamper visible indicator for container lid |
US4519515A (en) * | 1982-12-21 | 1985-05-28 | Milton Schonberger | Disc for indicator for tamper-evident lid |
EP0111900A3 (en) * | 1982-12-21 | 1985-07-31 | Milton Schonberger | Tamper visible indicator for container lid |
WO1984003270A1 (en) * | 1983-02-18 | 1984-08-30 | Tri Tech Syst | Tamper evident closures and packages |
US4489841A (en) * | 1983-02-18 | 1984-12-25 | Tri-Tech Systems International, Inc. | Tamper evident closures and packages |
US4905851A (en) * | 1983-02-18 | 1990-03-06 | Tri-Tech Systems International, Inc. | Tamper evident closures and packages with color changing means and separable portions of the closures and method of forming the same |
US4454956A (en) * | 1983-05-16 | 1984-06-19 | Minnesota Mining & Manufacturing Company | Tamper indicating composite tape closure |
US4505399A (en) * | 1984-06-21 | 1985-03-19 | Weiner Robert C | Tamper-indicating device and method |
US4781323A (en) * | 1985-08-27 | 1988-11-01 | Minnesota Mining And Manufacturing Company | Reclosable closure assembly for container |
USRE33893E (en) * | 1985-08-27 | 1992-04-21 | Minnesota Mining And Manufacturing Company | Reclosable closure assembly for container |
US4715528A (en) * | 1985-09-20 | 1987-12-29 | Tetra Pak International Ab | Reclosable opening arrangement on a packing container |
US4720423A (en) * | 1986-08-25 | 1988-01-19 | Minnesota Mining And Manufacturing Company | Package opening system |
US4874096A (en) * | 1987-07-02 | 1989-10-17 | Sales S.P.A. | Sealed packet with an adhesive strip for opening and reclosing |
US4911302A (en) * | 1988-02-01 | 1990-03-27 | R. J. Reynolds Tobacco Company | Method for imprinting overwrapped packages |
US4865198A (en) * | 1988-02-01 | 1989-09-12 | R. J. Reynolds Tobacco Company | Overwrapped package with tamper indicating means |
US5020831A (en) * | 1988-12-23 | 1991-06-04 | Arysearch Arylan Ag | Imprinted product with tamperproof seal method of producing product |
US5153042A (en) * | 1989-05-16 | 1992-10-06 | Minnesota Mining And Manufacturing Company | Tamper-indicating labelstock |
US4986429A (en) * | 1989-06-12 | 1991-01-22 | Singleton Jr Robert | Color indicating tamper-proof seal |
WO1991019649A1 (en) * | 1990-06-20 | 1991-12-26 | Alcan International Limited | Color change devices activatable by bending |
US5135262A (en) * | 1990-06-20 | 1992-08-04 | Alcan International Limited | Method of making color change devices activatable by bending and product thereof |
US5282650A (en) * | 1990-06-20 | 1994-02-01 | Alcan International Limited | Color change devices activatable by bending |
US5152412A (en) * | 1990-07-18 | 1992-10-06 | Continental White Cap, Inc. | Tamper evident closure using microcapsules |
US5312680A (en) * | 1991-02-25 | 1994-05-17 | Carolyn N Simpson | Tamper-revealing sealing device for packaged documents |
US5234732A (en) * | 1991-03-18 | 1993-08-10 | Philip Morris Inc. | Tamper-indicating wrappers |
US5219194A (en) * | 1992-02-28 | 1993-06-15 | Viking Corporation | Security seal |
US5325721A (en) * | 1993-02-17 | 1994-07-05 | Minnesota Mining And Manufacturing Company | System for indicating exposure to preselected temperatures or tampering |
GB2280402A (en) * | 1993-07-19 | 1995-02-01 | Roger William Middleto Bromley | Bleeding tape |
GB2280402B (en) * | 1993-07-19 | 1996-07-03 | Roger William Middleto Bromley | Bleeding tape |
WO1995013229A1 (en) * | 1993-11-10 | 1995-05-18 | Carnaudmetalbox Plc | Closures for containers |
US5631068A (en) * | 1994-08-02 | 1997-05-20 | Trigon Packaging Corporation | Self-containing tamper evident tape and label |
US5798169A (en) * | 1994-08-02 | 1998-08-25 | Sealed Air Corporation | Self-containing tamper evident seal |
US6531528B1 (en) * | 1999-05-05 | 2003-03-11 | Dap Products Inc. | Ready to use spackle/repair product containing dryness indicator |
US6609865B2 (en) | 2001-12-24 | 2003-08-26 | Ipex Inc. | Color pressure-sensitive fastener |
US20050023821A1 (en) * | 2002-06-25 | 2005-02-03 | Appleton Papers Inc. | Product authentication |
US20030236165A1 (en) * | 2002-06-25 | 2003-12-25 | Appleton Papers Inc. | Product authentication |
US6939826B2 (en) * | 2002-06-25 | 2005-09-06 | Appleton Papers, Inc. | Product authentication |
WO2004035400A2 (en) | 2002-10-18 | 2004-04-29 | Alcan International Limited | Containers with peelable closures that change appearance upon bending |
US20040150221A1 (en) * | 2003-01-30 | 2004-08-05 | Brady Worldwide, Inc. | Tamper evident seal |
US7682696B2 (en) | 2004-09-13 | 2010-03-23 | Sabic Innovative Plastics Ip B.V. | Medical article and method of making and using the same |
US20060054526A1 (en) * | 2004-09-13 | 2006-03-16 | Jennifer Dean | Medical article and method of making and using the same |
US7913870B2 (en) | 2005-05-10 | 2011-03-29 | Pactiv Corporation | Tamper evident container |
US20090093063A1 (en) * | 2007-09-07 | 2009-04-09 | Anslyn Eric V | Color Changing and Coverage Indicating Hand Sanitizer |
US20100224630A1 (en) * | 2009-03-06 | 2010-09-09 | Petlak Frank A | Tamper Evident Container With Pull Tab |
US10220986B2 (en) | 2009-03-06 | 2019-03-05 | Pactiv Corporation | Tamper evident container with full tab |
US20150004706A1 (en) * | 2013-06-26 | 2015-01-01 | Mridula Nair | Reactive indicator compositions and articles containing same |
US20150004707A1 (en) * | 2013-06-26 | 2015-01-01 | Mridula Nair | Methods for using indicator compositions |
US9289528B2 (en) * | 2013-06-26 | 2016-03-22 | Eastman Kodak Company | Methods for using indicator compositions |
US9291570B2 (en) * | 2013-06-26 | 2016-03-22 | Eastman Kodak Company | Reactive indicator compositions and articles containing same |
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US20180322812A1 (en) * | 2015-02-24 | 2018-11-08 | Validation Security Technology Identification S De Rl De Cv | Smart label system |
US11124332B2 (en) * | 2018-07-31 | 2021-09-21 | Ynb Supply (Asia) Corporation | Ring-peel-seal liner |
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