AU690542B2 - Single ply PSA labels for battery applications - Google Patents
Single ply PSA labels for battery applications Download PDFInfo
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- AU690542B2 AU690542B2 AU63913/96A AU6391396A AU690542B2 AU 690542 B2 AU690542 B2 AU 690542B2 AU 63913/96 A AU63913/96 A AU 63913/96A AU 6391396 A AU6391396 A AU 6391396A AU 690542 B2 AU690542 B2 AU 690542B2
- Authority
- AU
- Australia
- Prior art keywords
- backing
- battery
- label
- edges
- case
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- 239000010410 layer Substances 0.000 claims description 91
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 39
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 239000000853 adhesive Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000002093 peripheral effect Effects 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 229920006254 polymer film Polymers 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000003522 acrylic cement Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 241000566145 Otus Species 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000010276 construction Methods 0.000 description 24
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000000976 ink Substances 0.000 description 7
- 238000002372 labelling Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920006257 Heat-shrinkable film Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- AQWSFUIGRSMCST-UHFFFAOYSA-N 3-pyridin-3-ylsulfonyl-5-(trifluoromethyl)chromen-2-one Chemical compound N1=CC(=CC=C1)S(=O)(=O)C=1C(OC2=CC=CC(=C2C=1)C(F)(F)F)=O AQWSFUIGRSMCST-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
- G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
- H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Primary Cells (AREA)
Description
WO 96/42115 1 1 CT/US96/1076) SINGLE PLY PSA LABELS FOR BATTERY APPLICATIONS Background of the Invention Dry cell batteries are the most popular portable sources of electrical energy. They include flashlight, tool, toy, appliance batteries, and the like. Dry cell batteries come in a variety of configurations and voltage outputs and may be single or multiple use batteries.
The most popular sizes are the "AAA," and "9 volt" batteries. The AA, AAA, C and D size batteries, along with some other configurations utilize at least one drawn metal cylindrical casing providing and serving as the positive end pole and an end serving as the negative pole. The positive pole is separated from a negative pole by an insulator.
In early batteries, graphics used to present battery information to the consumer were applied on the battery case. Graphics were next presented on metallized paper coverings for the case of the battery. The latter has now been largely supplanted by labels which are based on the use of multiple layers or plies of polymeric shrink films, with the most popular polymeric material being polyvinyl chloride. The multilayer constructions employed have been what is termed in the art "triplex" and "duplex" constructions with triplex being the most common.
With reference to the drawing captioned "Prior Art," the triplex construction consists of a composite laminate of a first heat shrinkable, self-supporting, polymeric polymer film layer on which there is applied a layer of a metal normally formed by vapor deposition onto which there is added a second self-supporting, heat shrinkable, polymeric film layer a graphics layer and a top protective layer of another self-supporting, heat shrinkable polymeric film layer A pressure-sensitive adhesive layer is applied to the undersurface of film layer In the duplex construction, the first intermediate heat shrinkable polymer layer is eliminated to provide a laminate of a first heat shrinkable polymer film layer onto which there is provided a metallized layer pigmented layer and the heat shrinkable polymer layer Again heat shrinkable polymer film layer is undercoated with the pressure-sensitive adhesive layer In either constructions where a bond is weak, particularly between a self-supporting, heat shrinkable polymer layer and a layer of metal, it has been common to utilize a layer of adhesive to enhance the strength of the bond.
Multilayer adhesive label constructions are described for instance in U.S. Patents 4,801,514, 4,911,994, 5,032,477, 5,262,251 and 5,312,712, to Will et al. each incorporated herein by reference.
Attempts have been made to move the layer of metal from between layers of -self-supporting heat shrinkable polymeric film to between a heat shrinkable polymer film layer and the layer of a pressure-sensitive adhesive. One such construction, not involving -1- SUBSTITUTE SHEET (RULE 26) WO 96/42115 PCT/US96/10769 I the use of shrink polymeric films, is described in U.S. Patent 5,292,566 to Sharklett, III incorporated herein by reference. A significant limitation of this construction, however, is that the bond of the metal to the polymeric layer is weak and the layer of metal has been susceptible to cracking by on-line impact forces used to impart lot and date code information to the label. Segments of the broken layer of metal has been known to penetrate the relatively soft pressure-sensitive adhesive layer and short circuit the battery causing dissipation of electrical energy.
Another approach which has been commercially tried has been to substitute a UV cured varnish for the top layer of heat shrinkable polymeric film This construction is described in U.S. Patent 5,190,609 to Lin et al. incorporated herein by reference. These labels have found only limited acceptance, as the coating has proven to be a weak link exhibiting poor abrasion resistance and resistance to changes in environmental conditions.
Multiple layer constructions also present problems of matching the shrink characteristics of the several polymeric films so that no slip occurs between adjacent heat shrinkable polymeric film layers on heat shrinkage. If not, distortion of graphics, puckering and possible delamination can occur. The duplex construction has also exhibited problems of liftoff of the label from the battery case as well as poor environmental aging.
It would be desirable to provide a pressure-sensitive adhesive single ply construction for wrapping the casing of a battery. A single ply construction would be cheaper than multiple layer label constructions now employed.
A single ply battery label to be functional has to have a service life in excess of years without exhibiting losses due to the environmental stress, including cyclic exposure to temperatures in excess of 150'F and humidities approaching 100%. More significantly a single ply label must properly withstand the rigors of manufacture without benefit of the presence of other plies whose characteristics can be used to add to or modify the characteristics of a single ply to account for manufacturing and environmental stresses.
In consequence, providing an effective single ply label remains an ongoing quest in the art, despite cost and production advantages as well as an advantage in that a single ply label construction maximizes functional battery volume by reducing the thickness of the label, thereby allowing the battery manufacturer to pack more energy into a total battery construction of fixed external dimensions.
Summary of the Invention There is provided in accordance with the instant invention single ply labels for dry cell batteries which provide a peripheral shell and opposed ends enclosing a direct current electrical energy providing core. The label is formed of a transparent, self-supporting, monoaxially oriented, heat shrinkable polymeric film facestock or backing having a width and length. The width of the backing provides at its ends first and second opposed longitudinal
-I
WO 96/421 15 PCT/US96/10769 1 edges and is sufficient for the backing to embrace the case of the battery so that the first and second edges meet in at least abutting relation. The length of the backing is sufficient for the backing to extend beyond the length of the battery case and provides at its ends first and second opposed peripheral edges adapted, when wrapped about a battery case, to extend beyond the length of the battery case. An opaque alkali resistant, electrically non-conductive pigmented layer covering any visual indicia printed on the undersurface of the backing is also printed on the undersurface of and supported by the backing. An electrically non-conductive pressure-sensitive adhesive layer extends at least along the length of the first and second edges of the backing, preferably about the periphery of the backing and extending sufficiently inward from the several opposed edges of the backing to ensure adhesive contact with the peripheral case of the battery at least at each opposed end of the battery. It is preferred that the pressure-sensitive adhesive extend over the entire pigmented layer. The pressure-sensitive adhesive has sufficient shear or cohesive strength to prevent heat shrinkage of the backing at least about the periphery of the battery and a sufficient peel adhesion to prevent lifting of the label from the case of the battery along the length of the battery.
The label is applied to the outer surface of the case of the battery and attaches to the case by contact of the pressure-sensitive adhesive. The label is then wrapped around the battery case with first and second edges at least abutting third and fourth edges protruded beyond the battery case. The protruding ends of the label are caused by action of heat on the heat shrinkable film to shrink to wrap over the opposed ends of the battery.
The pigmented layer is for purposes of this invention, considered to be alkali resistant if impervious to the action of 7.2N KOH for 24 hours in an immersion test and electrically resistant if resistance is greater than about 560 megohms (560 x 106 ohms).
The presently preferred adhesive is a solvent based acrylic, pressure-sensitive adhesive. Emulsion or hot minelt pressure-sensitive adhesives may also be effectively employed. It is presently prererred that the pressure-sensitive adhesive provide a peel strength or peel adhesion of at least about 2 Pli (pounds per inch), preferably about 2 to about 5 Pli, a shear strength of at least 4,000 mins., preferably from about 4,000 to about 10,000 mins. and a loop tack of at least about 2 Pli, preferably about 2 to about 4 Pli The preferred backing has a coefficient of shrinkage in the peripheral or circumferential direction of up to about 60%, preferably about 20% to about 60%, more preferably about 40-50%. Shrinkage is along the width of the backing, modrine direction. The presently preferred backing is a transparent, monoaxially oriented polyvinyl chloride film about 2 mils. thick.
I M WO' 96/42115 PCT/US96/10769 1 Brief Description of the Drawings That portion of the drawings captioned "Prior Art" illustrates triplex and duplex label constructions which represent current adhesive battery label constructions, FIG. 1 illustrates a prospective view of the detail of the layers of the single ply label of the instant invention along with the relationship of the label to the battery case.
FIG. I-A shows the same construction as FIG. 1 except where the adhesive layer extends around the periphery of both the label.
FIG. 2 shows the single ply label of the instant invention wrapped about the circumference of the battery in abutting relationship.
FIG. 3 illustrates heat shrinkage of protruding ends of label over opposed ends of the battery by the application of heat.
FIG. 4 illustrates one means for labeling batteries using the single ply labels of the instant invention.
I WO 96/42115 PCTI/US96/ 0769 1 Detailed Description In accordance with the instant invention, there is provided single ply labels for dry cell batteries and batteries clad with such labels.
Batteries to be clad with the single ply labels of the instant inventions include cylindrical "AA" "AAA" and and size batteries. Labels used for such batteries exceed battery length and enable label ends, when shrunk, to fold over and onto opposed ends of a battery. Labels of the instant invention may also be employed for any other dry cell battery construction which does not require the electrical considerations of cylindrical AA, AAA, C and D size batteries. Other such battery configurations include but are not limited to the popular 9-volt batteries.
With reference now to FIGS. 1, 1-A, 2 and 3, a typical cylindrical dry cell battery consists of an electrical energy providing core 12 preferably formed an alkaline material and electrode 14. Both are cased by cylindrical shell 16 providing a positive pole end cap terminal 18 and negative pole end cap terminal 20. The positive pole is electrically connected to the core 12 and the negative pole is electrically connected to the electrode 14.
Case 16 is electrically insulated from end cap 20 by an annular insulator 22 of a suitably non-conductive material. Portions of positive and negative end cap poles 18 and 20 are in contact within the single ply battery label 24 of the instant invention.
As depicted in FIG. 1 and 1-A, the single ply battery label 24 consists of three principal layers: a self-supporting, heat shrinkable layer 26; a supported alkali resistant pigmented layer 28, which is electrically non-conductive at least in regions where it extends over battery segments 16 and 20 of the battery case; and, a supported, pressure-sensitive adhesive layer 30, which is electrically non-conductive, at least where it extends over elements 16 and 20 of the battery case. Pressure-sensitive adhesive layer 30 must extend along first and second edges 32 and 34 shown to be parallel to the axis of the battery. Edges 32 and 34 are to abut and may overlap. Adhesive is provided to ensure some pressure-sensitive adhesive at each of the four edges contacts the batteiy case. Desirably, as shown in FIG. I-A, the pressure-sensitive adhesive extends about the periphery of label 24, provides first and second edges 32 and 34 and third and fourth edges 36 and 38, More typically, as shown in FIG. 1, the pressure-sensitive adhesive layer 30 extends over the entire surface of layer 26. The pressure-sensitive adhesive layer 30 is at least electrically non-conductive where it contacts elements 18 and 20 to prevent drainage from the positive pole to the negative pole of the battery. Pigmented layer 28 and the heat shrinkable polymer facestock or backing 26 are also electrically non-conductive where they are in electrical contact with both poles of the battery 10. The non-conductive pigmented layer which eliminates prior fragile vacuum deposited metal layers is critical to the use of a single layer support.
1. WO 96/42115 PCT/US96/1 0769 1 Another key to the ability to provide a single ply battery label is the proper choice of facestock with production parameters in mind. There must be achieved with a single selfsupporting layer, namely, the facestock on which the graphics are underprinted and over such underprinted graphics the adhesive is applied, a net construction which must perform as are equivalent of multiple layers which have been employed in the past. In the past, in employing multiple self-supporting layers, one layer could complement another or modify or enhance certain property in order to tailor the label to the vigors of manufacture. In the present invention, a single layer must provide function of multiple layers and still minimize label thickness. This cannot be achieved at the sacrifice of production. For, if going to single layer significantly increases production cost the increase of production cost will overcome the advantage of the single layer. In addition, the single support film must be thermally shrinkable and yet be sufficiently inelastic to withstand distortion at repeated registrations at various printing sites where a plurality of colors used to form informational as well as esthetic graphics are printed. For such operation, some 6 to 10 or more colors will be added to a film. The film must not adversely stretch or else there will be shifts in registration impeding print clarity which will be commercially unacceptable. At the same time, the film must have some degree of shrinkage in the machine direction to enable the ends of the applied labels to fold over the end of the battery on appiication of heat without distortion of the graphics on the film. If there is excessive drawback or shrinkage, the film could lift at the seams exposing adhesive which would be a source to collect dirt, another unacceptable result. In addition, improper shrinkage of the seams could result in lift which leads to undesirable cosmetic appearance. With these goals in mind and the production rates of up to 800 batteries per minute for "AA" size and 600 or more batteries per minute for "AAA" batteries in labeling machines, the following specifications have been arrived for the self-supporting layer of the label construction.
Facestock or backing 26 is for the single ply construction is a monoaxially oriented polymer film, which is oriented substantially only in the direction normal to the axis of the battery, i.e. along the backing width and about its periphery. Shrinkage in that direction, in the machine direction or in the direction from first edge 32 to second edge 34 may, depending on production rate, be up to about 60% generally from about 20 to about and preferably range from about 40 to about 50%, most preferably from about 40 to about for smaller batteries and 40 to 50% for larger batteries.
Residual shrink-back in storage should be not more than about 10%, preferably less than more preferably less than about 3%.
Some shrinkage may also occur in the axial direction normal thereto. Shrinkage in one direction to a direction normal thereto is from -2 to 5 preferably 0-3 even more preferably about A negative shrinkage means elongation.
r I M WO 96/42115 PCT/US96/10769 1 The presently preferred mechanical properties of the film are tinsel strength of about Kpsi in the machine direction, an elongation of 77% in the machine direction and elastic modules of 400 Kpsi in the machine direction all according to ASTM D882-91 (Test Method
A).
A presently preferred heat shrinkable film layer 26 is preferably about 2 mils. thick and a substantially monoaxially oriented polyvinyl chloride film having a manufactured by American Mirrex Corp. of New Castle, Delaware.
Presently preferred films are machine direction monoaxially oriented polyvinyl chloride films having a thickness of from about 1 to about 3 mils., preferably from about 2 to about 3 mils., more preferably about 2 to about 2.5 mils.
In addition to polyvinyl chloride films other heat shrinkable films which may be used as the facestock include, but are not limited to, polyvinyl fluoride films, vinylidine fluoride films, polypropylene films and the like. Other films include polypropylene films described in U.S. Patent 5,190,609 to Lin et al. incorporated therein by reference. Facestock 26 serves as the self supported carrier for pigment layer 28 and pressure-sensitive adhesive layer Between pigment layer 28 and film 26, there are contained other intelligent indicia formed of inks such as decorative graphics, bar codes, product information and the like.
While surface conductivity and alkali resistance is not critical to such inks, they are preferably provided as inks which display resistance to attack by alkali (KOH) and preferably an electrical resistance at least equal with the electrical resistance of the pigmented layer 28 and/or pressure-sensitive adhesive layer 30. This eliminates any consideration of minor flaws providing short circuit battery drainage where the elements of label, facestock, pigmented layer and pressure-sensitive adhesive layer are in electrical contact with both the positive and negative polar elements of a battery.
As to any layer of the label which contacts the opposed poles of a battery, it is required that such layer be essentially non-responsive to the action of alkali or be alkali-resistant. By "alkali-resistant" there is meant the absence of any perceptible change in appearance upon exposure to 7.2N KOH for about 24 hours. Any of the element 28 and 30 which electrically contact positive and negative battery elements must also be electrically non-conductive. By "electrically non-conductive" there is meant a resistance greater than about 560 meg ohms (560 x 106 ohms). While only components of a layer which, by necessity, bridge positive and negative poles of a battery must be electrically non-conductive, it is, as stated above, prefeTrred that all of layers 28 and 30 be electrically non-conductive, Pigmented layer 28 is formed of alkali resistant inks in which the pigment is deposited from a carrier or vehicle to leave an alkali resistant, electrically non-conductive layer which is supported by backing 26 and which prcvide a coating which is opaque and forms a background for a label. Single color and multicolor, side by side or overlapping pigmented I- WO 96/42115 PCT/US96/ 10769 1 layers may comprise layer 28. The indicia and background forming pigmented layer 28 are underprinted on the self-supporting, transparent layer 26.
Presently preferred alkali resistant electrically non-conductive inks are manufactured by Zeneca Specialty Inks, Dayton, New Jersey. Suitable are Zeneca NDX-1467, (copper), NSX-1442 (silver), NKX-2155 (black) and NWX1596A (white). Copper and silver color inks have a pearlescent formulation, which provides a metallic appearance alvd, replaces the conductive layer of metal found in the prior art label constructions. It is presently preferred that pigmented layer 28 be continuous over the back portion of the transparent film 26 of label 24. As indicated, however, it can be discontinuous or multilayered provided that the portion of the pigment layer 28 which is in electrical contact with the positive and negative poles 20 and 22 be electrically non-conductive in addition to being alkali resistant.
Pressure-sensitive adhesive layer 30 may, as shown in FIG. 1, extend over the entire surface of the film 28. It may also extend only along edges 32 and 34 or, as shown in FIG.
l-A, extend about the periphery of label and be of a width sufficient to ensure contact with the case of the periphery of the battery. The adhesive bond to the battery case should be sufficient to ensure that no shrinkage of the label will occur between zones of adhesive contact except where the label extends beyond the ends of the battery. With reference to FIGS. 2 and 3, on exposure to heat the extended ends shrink, fold over and are adhered by the pressure-sensitive adhesive to the opposed ends of the battery. In the event the pressure-sensitive layer 30 only runs along edges 32 and 34 forming seam 42, graphics must be designed to account for the manner in which layer 26 shrinks in the axial direction.
The pressure-sensitive adhesive may be applied from a solvent, emulsion or suspension or as a hot melt. The pressure-sensitive adhesive must have sufficient shear or cohesive strength to prevent excessive shrink-back of the label where adhered to the battery case upon the action of heat after placement of the label on a battery as the substrate; sufficient peel strength to prevent the facestock from lifting from the battery and sufficient tack or grab to enable adequate in flight attachment to the label to the battery case during the labeling operation.
The presently preferred pressure-sensitive adhesive is of a solvent based acrylic adhesive manufactured by Ashland Chemical Company, Columbus, Ohio, under the product designation 1860Z45 modified with an addition of an antioxidant. Another suitable solvent acrylic pressure-sensitive adhesive is PolytexM 7000 manufactured by the Avery Chemical Division of Avery Dennison Corporation and described in U.S, Patent 4,812,541 to Mallya et al. incorporated herein by reference. A suitable emulsion pressure-sensitive adhesive is that described in US. Patent 5,221,706 to Lin et al. incorporated herein by reference.
In order to have an overall balance of adhesive properties and to enable proper application and retention of label intact on the battery case, it is presently preferred that the adhesive have a peel strength or adhesivity of at least preferably about 2 Pli, more preferably WO 96/42115 I'PCT/US96/10769 1 2 to about 5 Pli, width as determined by using PSTC #1 (Pressure-Sensitive Tape Counsel Test run at 12 inches per minute peel rate after 20 minute dwell on a 2-mil polyester backing; a shear strength, a measure of cohesive strength, of at least 4,000, preferably about 4,000 to about 10,000 minutes according to PSTC Test #7 using 2 mil polyester backing, which for a sample measuring 0.5 by 0.5" and a 500 gram weight, result is in a loading of 2,000 grams per square inch test and a loop tack of at least about 2, preferably 2 to about 4 Pli at a 12" per minute peel rate for a 1" wide loop on stainless steel.
FIG. 4 depicts one labeling operation. With reference thereto, labels 24 on web of release material 44 are caused to pass over a relatively sharp dispensing edge 46 and release from the web of release material 44, and adhere in flight and "grab" onto the surface of advancing battery 10. The battery 10 is rotated by roll 48 as it continues to advance, and label 24 is wrapped around the shell of the battery in abutting (FIG. or slightly overlapping relation to form seam 42. The pressure-sensitive adhesive layer 30 contacts the cylindrical portion of the shell of the battery. The label is secured rigidly to the battery case and acts to resist label shrinkage about battery case and preferably along the length and width of the battery case on application of heat from source 50, normally an air knife. The adhesive also prevents distortion of any indicia contained between layers 26 and 28 due to heat shrinkage of the facestock 26. Elimination of adhesive from along edges 36 and 38 is feasible if the backing has low shrinkage in the direction of the battery axis.
With further reference to FIG. 2 and 3, once the labels have been rolled about and adhered to the cylindrical shell of battery 10, the ends 40 of the label extend beyond the cylindrical case of battery 10 a,:d protrude beyond the positive pole 18 and the negative pole (not shown) of battery 10, As shown in FIG. 3, on application of hea, the label shrinks causing the label end to wrap over the positive and negative poles of the battery causing, when present, the pressure-sensitive adhesive to adhere the. label to the battery case at the two ends. In the alternative, the shrinkage may be sufficient to hold the overlapping portions of the label against the surface of the ends of the battery. In the above embodiments, cohesive strength of the pressure-sensitive adhesive insures that label movement due to shrinkage along the cylindrical case does not occur and as a consequence, distortion of the indicia cannot occur nor in any instance there will not form an opening at seam 42 in consequence of circumferential shrinkage, In sum, the graphics remain intact while, upon shrinkage, the exposed ends are drawn by heat shrinkage to and adhered by the pressure-sensitive adhesive to the positive and negative poles of the battery completing, at low cost, battery labelling.
Claims (18)
- 2. A single ply label as claie nclaI In which thebackng hasa hrinkage of about 40 to about 50% In the direction along tlw width of the backing. 3, A single ply label as claimedlInclaim 1 inwhicht backing has ashrinkage of about 40 to about 45 In tdo direction along t width of the backing.
- 4. A single ply label asclamed in clai 1, 2or 3 Inwhich the backcingbhas forme of a monoaxially oriented polyvinyl chloride film and having a thicknes of about I to about 3 milis. I :eceived Event (Event Succeeded) POGT/ U S 96/ 7 6,9 Date: 9/11/97 Time: 8: 37 FWWA'U) E.1 S tP 19 Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 17:36 TO-917033053599 FROH- Type: Fax T-092 K.08/20 F-170 1 5. A single ply label as clatnedin claims1,2 or 3in whch the backng h" formed of a mnoaxially oriented polyvinyl chloride film and baving a thickness of abou 2 to about mils.
- 6. A single ply label aclaimedIn any oneaofclalmI to 5in whichthe pressure-sensitive adhesive Is an acylic based adhesive having a peel strength of At leadt about 2 Pli, a ahear strength of at least 4,000 Minutes and a loop tack of at least about 2 P11 at 12 inch per minute peel rate far a I inch loop on stainless stal. Ia7. A singoply label as clahedIn any oneofclilms Iro 5inwhich the preure-ensitive adhesive is an acrylic based adhesive having a peel strength of at least 2 to about 5 P11 and a shear strength of at least of about 4,000 to 10,000 mrnutes.
- 8. A single ply label as clahned in any one of the previous claim int which tMe pressure-sensitive adhesive additionally extends along the third and fourth edges of the backing.
- 9. A single ply battery a claimed In any one of the previous claims In which substantially all of the pigmented layer Is covered with the pressure-menItive adhesive layer. A single ply label for lating a dry cell battery as claimed In any one of the previous claims In which Bald label comprisoes- an at least partially tansparent, self supporting, substantially monoaxially oriented, beat shrinkable polymer f backing having an outer sui1fe ua an lnae surfa for facing the battery rase. a thickness of about 1 to about 3 suils, a width providing at opposed ends thereof, first and second edges for extending parallel to the axis of t batey, and a length for extending beyond the length of t battery and providing at opposed ends teof third and fourth edges for extending normal to the axis of te battery, the width of the backing being sufficlent for the backing to embrace t peripheral shall of the battery and for "h fiast and second edges to meet In at least abutting relationship ;tbout the peripheral case of the battery, and the length of the backing being sufficient for the third and fourth opposed edges to lap over the opposed ends of the battery on heat shrinlage of the backing, said backing having a heat shrnka predominantly In the direction of the backing and In an amount of vp to about 60% In the direction of the width of the backins; an opaque pigmeunted layer comprised of an alkali resistant, electrically non-conductive Ink: applied to the Inner surface of and supported by the backing, said layer exhibiting no perceptible change upon exposure to the action of 7,2N KOH for 24 1 =us; and :eceived Event (Event Succeeded) 6 7'9 Date: 9/11/97 Time: 8:37 J/ Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 1737 TO-917033053599 FRType: Fax T-092 P.09/20 F-170 I(c) an electrically non-cornductive, acrylic based, presure-sensifive Adhesive layer extending over the pigmentcd layer at least along the frst And second edges A having a peel strength of at leat about 2 PH1 and suileciet to proven lifing of tha applied label from the case of the battery and a shear strength of At lenst about 4,000 minutes and sufficient to preventmovmntofn adivlyappled frst -dge of the backing to the caserelative to an adhesively applied second edge of the backing 9n hear shrinkage of an adhesively applied backing. 11, Asingle ply label asclaied inclam0 n whchthe backing has formed of a monoaxially orited polyvinyl chloride Mim And having a thickness of about 2 to about mnils and a shrinkage of About 40 to 45% In the direction of the width of the backing. 12, A labeled dry-cell battery having an elongato peripheral case defining an axis and opposed ends Intersecting the axis And enclosing, with the case, a direc electrical energy providing core, said label formed of: an at leas partially transparif heat shrunk, self supportin, nionoaxially oriented, polymer fllm backing having an outer surfc AnM an inner surfac facing the battery case, a width terminating in opposed first and second edges extending parallel to the axis and a length termiinisting in opposed third And tburth edges extending normal to the axis, said first And secondl edges secured by a pressur-sensitive adhesive to rhe case 0,f the battry at least substantially abutting relationship, each of said first and second edges substat~uy prevented from movement relative to the other on heat shrinkage of the backing about t battery case, said third and fourth opposed edges lapping onto and beat shrunk against the opposed ends of the battery, said backing having a heat shrinkage predominantly in the direction of the width of the backing and in an amount up to About 60% In the direction of the width of the backing prior to heat shrinkage; an opaque pignted layer comprisod of an Alkali resistant, elecricaily non-conductive Ink applied to the inner 8urtac of and suipported by the backing, said layer exhibiting no perceptible change upon exposure to t Action of 7.2N KOH for *24 hours: an an electrically non-conductive pressure-sensitive adhesive layer adhering the label to the battery case and applied to and extending over the pigmented layer at least along the frt and second edges and extending sufficiently hnwar of the first and seond edges to adhere to the battery case and having a peel Adhesion of, for example 2 PH and suffIrtient to substantially prevent lifting of the first and second edges from the came of the battery and a shear strength, for example at least 4,00 minutes and sufficient to substantially prevent movement of the first edge of the backing relative to t second edge of t backIng on heat shrinkage of the backing. -12- .1 RA4/; eseived Event (Event Succeeded) P oTus q&LJ/inLZL199 Date: 9/111197 Time: 8:37 Ii E?19 Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 17:37 T0-917033053M9 FROM- Type: Fax T-092 P. 10/20 F-170 1 13. A battery as claimed in claim 12 in which the monoaxially oriented backing Is, priortosrne, upto about6% shinked ite irectolog he witofthe backing.
- 14. A battery as clamdin clai12in whchthe maxiallyoriented bckng it prior to shrinkage about 40 to about 50% shrnkable In die direction along the width of the backing. Abattr asclaimed inclaim 12, 13or14 Inwhich thebacking isforadof a inonoaxially oriented polyvinyl chloride film and hav"n a thickness of about 1 to about 3 mils. to
- 16. A battery as claimed in any one of claims 12 to 15 in which the backcing Is formned of a monaxially oriented polyvinyl chloride film and having a thickness of about 2 to about mils and has a shrinkage of about 40 to about 45 In the direction along the width of the backing.
- 17. A battery as claimed in any one of claim 12 to 16 in which the pivssuresensitive adhesive has a peel strength of at leant about 2 PH1, a shear suregth of at least about 4.000 minutes and a loop tack of at least about41 P11 at at 12 inch per minute peel rate for a 1 Inch loop on stainless steel.
- 18. A battey as clamedIn any owof clais2 to7 in whchhepressure-enilve adhesive Is an, acrylic adhesive having a peel strength of at leasn 2 to about 5 ?If a4M a shear strength of about 4,000 to 10,000 minutes, 19, A battery as clrd InAnyone ofclaims2 to 8In which the prmnaur-snslve adhesive additionally extand4 idong the third and fourth edges of the battery and at least adhesively secures said backing at aid third and fourth edges to the opposed ends of the battery.
- 20. A battey asliInany eoaim 12 to9nhich the p ssure-sensflve adhesive layer covers substantially aill of the pigmented layer and in which the backing, at least at said third and fourth edges, is ,.amalvely secured to the opposed ends of the battery,
- 21. A battrry as claimed in any omeof clabns 12 to 20 In which the prssur-nsitive adhesive layer cover s ubstanti ally all of the pigmented layer.
- 22. A batter as claimed In any one of claims 12 to 21 In which the label Is formed of. eceived Event (Event Succeeded) A 7 Date: 9/11/97 Time: 8:37 PPE Sf199 Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 17:3\ TO-917033053599 FROH- Type: Fax T-092 P.11/20 F-170 1 an at least partially trasparent, self supporting, substantially monoaxially oriented, heat shrinkable polymer film backing having an outer surface and an inner surface facing the battery case, a thickness of abot 1 to about 3 mils, a width terminating, at opposee ends, in first and second edges extending parallel to the axis, and a length terminating at opposed ends, in third and fourth edges normal to the axis of the battery, said label embracing the peripheral case of the battery with the first and second edges meeting in at least abutting relationship and adhered by a pressure-sensitive adhesive to the case of the battery, the third and fourth opposed edges overlapping onto and heat shrunk against the opposed ends of 'he battery, said backing having a heat shrinkage ofup to about 60% in the direction of the width of the backing prior to shrinkage of the backing, said backing having a heat shrinkage predominantly in the direction of the width of the backing and in an amount up to about in the direction of the width of the backing prior to heat shrinkage; an opaque pigmented layer comprised of an alkali resistant, electrically non-conductive ink applied to the Inner surface of and supported by the backing, said layer exhibiting no perceptible change upon exposure to the action of 7.2N KOH for 24 hours; and an electrically non-conductive, acrylic based, pressure-sensitve adhesive layer adhering the label to the battery case and extending over the pigmented layer at least along the first and second edges sufficient to enable adhering the label at about the first and second edges to the case of the battery, said pressure-sensitive adhesive having a peel strength of at least about 2 Pli and sufficient to substantdally prevent lifting of the applied label from the case of the battery and a shear strength of at least about 4,000 minutes and, sufficient to substantially prevent movement of the first edge of the backing relative to the second edge of the backing on heat shrinkage of the backing.
- 23. A mrthod of manufacture of a labeled battery which comprises: providing a dry cell battery, said battery having an el'gate peripheral case extending along the battery length and defining an axis and opposed po and negative pole ends intersecting the axis and enclosing, with the case, a direct current, electrical energy providing core: providing on a web having release surface at least one label formed of an at least partially transparent, self supporting, substantially monoaxially oriented, heat shrinkable polymer film backing having an outer surface and an inner surface for facing the battery case, a width, providing, at opposed onds thareof, first and second edgea for extending parallel to the axis of the battery, and a length for extending beyond the opposed ends of battery and providing at opposed ends thereof third and fourth edges for extending normal to the axis of the battery, the width of the backing being sufficient for the backing to embrace the peripheral case of the battery and for the first and second edges to meet in at least abutting relationship, and the length of the backing biing sufficient for the third and fourth opposed leceived Event (Event Succeeded) f' I~ Date: 9/11/97 Time: 8:37 PM, Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 17:38 TO-917D33053599 FROH- Type: Fax T-09 P.12/20 F-170 I edgetlap over thopposed en ofthebattery onet shrnkagef the bacing; said backing having a shdalage predominantly in the direction of width of backing of up to and in an amount to about 60 In the directon of the width of the backing; an opaque pigmented layer comprised of an alkali resistant electrically non-conductive Ink applied to the inner surface of and supported by the backing, said layer exhibiting no perceptible change upon exposure to the action of 7.2N KOH for 24 hours; and Qii an electrically non-conductive pressure-sensitive adhesive layer applied to and extending over the pigmented layer at leas along the fims and second edges, said to pressure-sensitive adheive having sufficient peel strength, for example 2 P11 and sufficlemn to substantially prevent lifting of an applied label from the case of the battery and sufflcient shear stregth, for' example 4,000 minutes and sufficient to substantily prevent mvernent of an adhesively applied first edge of the backing to the case relative to an adhesively applied second edge of the backing to the case on heat shrinkage of an adhesively applied backing. IS diq~nlng =id labkI fromn said web tbr amtclunnt to said peripheral case of said battery; cauwing said label to adhere to and wrap arouind said poripheral case and said first and second edges to meet in abutting or overlapping relation with said third and fourth edger extending over opposed ends of te battery forming overlapping extensions; causing by application of heat, heat shrinkage of said polymer film and said overlapping extension to wrap over the positive and negative poles of the battery. 24, A method as claimed In clain 23 in which said pressure-sensitive adhbesive extends to Wad third van fourth mufhme nd the overlapplng extensions provide on shrinkage become adhesively bonded to the positive and negative poles. A method as claimed W. claims 23 and 24 in which the label is dispensed by passing the label over a relatively sharp edge,
- 26. A method as claimed In claimi 25 in which the dispensed label adhere in flight by saidfirst or second edge to saidbatry caeandwpdounld saidbattery emby rotaing of the battery case about said axis. 27, A method as claimed in any one of claims 23 to 26 in which the beat provided to shrink t label is from an air knife. 28 A mthod as claimin anyoneof clais 23 to27 iwhchtb ackinlghas a shrinkage of about 4.0 to about 50% in the direction along the width of the backing. S. leceived Event (Event Succeeded) 9A /10 769 Date: 9/11/97 Time: 8:7Pf~~lSIISEP '997 Pages: 20 Sender: Fax Number: Subject: Company: SEP 11 '97 17:38 TO-917033053599 FROM- Type: Fax T-092 P.13/20 F-170 1 29. A mcthod as claimedIn any one of clals 23 to27in which the bacitlng has a shrinkcage of about 40 to about 45 in the direction along the width of the backing. A method as claimed in any one of claims 23 to 29 In whicli the backing baa S formed of a monoaxi ally oriented polyvinyl chloride film and havfn a thickiam of about 1 to about 3 mils,
- 31. Amehd asclaimen any o of cla3o to 29Inhch backng haa formed of a no~axially oriente polyvinyl chloridle filmn and haiving a thickness of about 2 to about 2,5 mils.
- 32. A mathod as claimed In any one of claims 23 to 31 in which t pressur-aitvo adhesive is an acrylic based adhesive having a peel strength of at least about 2 PH1 and a shear strength of at least 4,000 minutes and a loop tackc of at Jew~ about 2 PH at a 12 inch per minute peelirate for a I inch loop on stainless steel.
- 33. A method as claimed in any one of claims 23 to 31 in which doe pieauresesitve adhesive is an acrylic based adhesive having a peel strength of at least 2 to about 5 PH1 and a shear strength of at least of about 4,000 to 10,000 minutes.
- 34. A method as claimed in any one of claim 23 o 33 in whichsubsumntally all of the pigmented layer is covered with the pressure-sensitive adhesive layer. Ubeled batteries whenever formed byt nmrd or any one ofclais23 to 34.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US480183 | 1990-02-13 | ||
US48018395A | 1995-06-07 | 1995-06-07 | |
US08/656,438 US5747192A (en) | 1995-06-07 | 1996-05-31 | Single ply PSA labels for battery applications |
US656438 | 1996-05-31 | ||
PCT/US1996/010769 WO1996042115A2 (en) | 1995-06-07 | 1996-06-07 | Single ply psa label for battery applications |
Publications (2)
Publication Number | Publication Date |
---|---|
AU6391396A AU6391396A (en) | 1997-01-09 |
AU690542B2 true AU690542B2 (en) | 1998-04-30 |
Family
ID=27046500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU63913/96A Ceased AU690542B2 (en) | 1995-06-07 | 1996-06-07 | Single ply PSA labels for battery applications |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP2001519962A (en) |
CN (1) | CN1146064C (en) |
AT (1) | AT407588B (en) |
AU (1) | AU690542B2 (en) |
CA (1) | CA2223952C (en) |
DE (1) | DE19681442T1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004230571A (en) * | 2003-01-28 | 2004-08-19 | Toppan Printing Co Ltd | Hologram label and its manufacturing method |
DE10309918A1 (en) * | 2003-03-07 | 2004-09-16 | Klöckner Pentaplast B.V., SM Weert | Plastic film made of hard polyvinyl chloride (HPVC) and process for its preparation |
JP2004319319A (en) * | 2003-04-17 | 2004-11-11 | Shin Kobe Electric Mach Co Ltd | Nonaqueous electrolyte secondary battery |
JP4561542B2 (en) | 2005-09-02 | 2010-10-13 | ソニー株式会社 | Secondary battery |
JP5551064B2 (en) * | 2007-05-10 | 2014-07-16 | ウーペーエム ラフラタク オイ | Battery label |
DE102010041143A1 (en) * | 2010-09-21 | 2012-03-22 | Sb Limotive Company Ltd. | Housing for galvanic element |
DE102011114136A1 (en) * | 2011-09-23 | 2013-03-28 | X-Label Gmbh - Holding | Method for labeling of shaped body i.e. package or product, involves attaching label and initializing return shrinking process of plastic film such that portions of label is spaced apart from shaped body and folds against contour of body |
JP5866939B2 (en) * | 2011-10-04 | 2016-02-24 | 日産自動車株式会社 | Electrical device |
DE102011088739A1 (en) * | 2011-12-15 | 2013-06-20 | Robert Bosch Gmbh | Housing for a battery cell with a paint coating for electrical insulation, battery cell, battery and motor vehicle |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4608323A (en) * | 1985-03-07 | 1986-08-26 | Duracell Inc. | Cell jacket |
JPH0576426A (en) * | 1991-09-24 | 1993-03-30 | Sekisui Chem Co Ltd | Sink stand |
US5443668A (en) * | 1993-02-19 | 1995-08-22 | Duracell, Inc. | Method for labeling an electrochemical cell |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4592973A (en) * | 1983-10-05 | 1986-06-03 | Castle Technology Corp. | Supported liquid membrane electrochemical separators |
US5194486A (en) * | 1989-06-09 | 1993-03-16 | H & N Chemical Company | Adhesive |
US5210141A (en) * | 1989-08-15 | 1993-05-11 | Shin-Etsu Chemical Co., Ltd. | Delustered thermally shrinkable film |
-
1996
- 1996-06-07 AT AT0905596A patent/AT407588B/en not_active IP Right Cessation
- 1996-06-07 DE DE19681442T patent/DE19681442T1/en not_active Withdrawn
- 1996-06-07 JP JP50341497A patent/JP2001519962A/en not_active Ceased
- 1996-06-07 CN CNB961960000A patent/CN1146064C/en not_active Expired - Fee Related
- 1996-06-07 AU AU63913/96A patent/AU690542B2/en not_active Ceased
- 1996-06-07 CA CA002223952A patent/CA2223952C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4608323A (en) * | 1985-03-07 | 1986-08-26 | Duracell Inc. | Cell jacket |
JPH0576426A (en) * | 1991-09-24 | 1993-03-30 | Sekisui Chem Co Ltd | Sink stand |
US5443668A (en) * | 1993-02-19 | 1995-08-22 | Duracell, Inc. | Method for labeling an electrochemical cell |
Also Published As
Publication number | Publication date |
---|---|
DE19681442T1 (en) | 1998-07-02 |
CN1196139A (en) | 1998-10-14 |
MX9709854A (en) | 1998-08-30 |
JP2001519962A (en) | 2001-10-23 |
AU6391396A (en) | 1997-01-09 |
CA2223952A1 (en) | 1996-12-27 |
CN1146064C (en) | 2004-04-14 |
CA2223952C (en) | 2003-03-25 |
ATA905596A (en) | 2000-08-15 |
AT407588B (en) | 2001-04-25 |
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