EP0766546B1 - Lasermarkierbare plastiketiketten - Google Patents

Lasermarkierbare plastiketiketten Download PDF

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Publication number
EP0766546B1
EP0766546B1 EP95922091A EP95922091A EP0766546B1 EP 0766546 B1 EP0766546 B1 EP 0766546B1 EP 95922091 A EP95922091 A EP 95922091A EP 95922091 A EP95922091 A EP 95922091A EP 0766546 B1 EP0766546 B1 EP 0766546B1
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EP
European Patent Office
Prior art keywords
laser
coextrudate
core layer
label
opaque material
Prior art date
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EP95922091A
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English (en)
French (fr)
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EP0766546A1 (de
EP0766546A4 (de
Inventor
Donald Francis Kimes
Richard Cayle Adams
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Avery Dennison Corp
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Avery Dennison Corp
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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
    • B65C3/00—Labelling other than flat surfaces
    • B65C3/06—Affixing labels to short rigid containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
    • B65C9/00—Details of labelling machines or apparatus
    • B65C9/46—Applying date marks, code marks, or the like, to the label during labelling
    • 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
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/085—Sheets or tubes applied around the bottle with or without subsequent folding operations and glued or otherwise sealed to the bottle
    • 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
    • G09F2003/0201—Label sheets intended to be introduced in a printer, e.g. laser printer

Definitions

  • the present invention relates to flexible, plastic labels for use on flexible plastic bottles, which labels are both ink printable and laser-markable.
  • plastic labels for squeezable, flexible plastic bottles have been made from paper coated with pressure sensitive adhesives. More recently, plastics have replaced paper to a large extent for this purpose. Plastic labels tend to exhibit a higher degree of flexibility, squeezability and a greater resistance to water and other chemicals than paper. Accordingly, plastic labels are becoming increasingly popular for use on flexible plastic bottles.
  • Attaching flexible plastic labels to flexible plastic bottles is normally accomplished in one of two ways.
  • a pressure sensitive adhesive is applied to the label and the label attached to a previously formed bottle by pressure.
  • IMFL In Mold Film Label
  • the label is placed into the mold used to form the bottle by blow molding and the label incorporated physically into the plastic bottle itself as part of the blow molding operation.
  • a heat-activatable adhesive is normally applied to the label for firmly bonding the label to the bottle body.
  • flexible plastic labels are attached to flexible plastic bottles at high rates of speed.
  • typical industrial applications using pressure sensitive labels can process as many as 200 bottles per minute and even up to 600 bottles per minute.
  • typical industrial applications for IMFL 5 to 150 bottles per minute can be made with labels attached.
  • labels exhibit appropriate gross mechanical properties. In order that the labels can flex with the bottles to which they are attached, they obviously must exhibit suitable flexibility, at least in one direction (usually the transverse direction). Moreover, in order that they can be effectively used in the modern, high-speed industrial processes described above, the labels must also exhibit additional properties such as die cutability, matrix stripability, dispensability (i.e., with enough stiffness to be dispensed at high speed from a peel plate or handled for insertion in a mold) and the like. Also, pressure sensitive labels further need to be repositionable, i.e., when misapplied they can be easily peeled off the bottle in a single piece with all the adhesive remaining on the label.
  • the label body is made by coextruding a number of different plastic materials together to form a multilayer coextruded product.
  • a real advantage of this approach is that the main body of the film can be formulated to maximize the desired gross mechanical properties of the label, while the skin layers of the product can be tailored for accepting printing ink, for receiving adhesives or both.
  • titanium dioxide-coated mica particles Another material also known to impart laser markability to various types of plastics is titanium dioxide-coated mica particles. Such materials are sold, for example, under the name AFFLAIR® by E. Merk Company of Raway, New Jersey and MEARLIN® Lustre Pigments sold by the Mearl Corporation of New York, New York.
  • the present invention utilizes known laser marking technology to impart laser imprinted images to the unique, flexible, plastic labels made in accordance with the present invention.
  • These unique plastic labels are multilayer coextrudates which are produced by coextrusion of at least two different polymer materials to form a product with at least two and preferably at least three distinct polymer layers bonded together.
  • such products are composed of an inner core layer and at least one outer skin layer.
  • the product will have two outer skin layers, one on each side.
  • One of these outer skin layers is typically intended to be ink printable (hereinafter “printing skin”), and accordingly the material used to form this layer and the manner of its extrusion are selected to maximize its ability to accept and retain printing ink.
  • the other outer skin (hereinafter “bonding skin”) is intended for bonding or facilitating bonding of the label to a bottle.
  • the bonding skin layer can either be adapted to receive a subsequently applied adhesive or, in fact, may constitute the adhesive itself.
  • the bonding skin is preferably a material which promotes adhesion of the acrylic adhesive to the olefin core, for example, an olefin copolymer containing polymerized vinyl acetate.
  • a label having a highly olefinic core layer is intended to be attached by IMFL to a highly olefinic bottle made, for example, from HDPE (high density polyethylene)
  • the bonding skin layer can itself comprise the heat-activatable adhesive normally used for this purpose.
  • a homopolymer or copolymer of ethylene or propylene is a good example of an appropriate material, for this purpose.
  • the thickness of the inventive labels can vary widely. Typically, they range between 0.5 and 15 mils, more preferably 1 to 10 mils, even more preferably between about 2 and 5 mils, thick. Of this amount, the printing and bonding skins each occupy about 5 to 25 percent of the thickness of the label, more typically about 10 to 15 percent of the thickness of the label, while the core layer occupies the rest.
  • manufacture of the inventive labels involves production of a continuous sheet or web of the coextrudate, orientation of the web or sheet usually in a single direction (machine direction) only, and finally cutting or otherwise subdividing the web or sheet into individual, discrete labels.
  • the coextruded web or sheet after orientation is usually laminated to a release liner comprising the pressure sensitive adhesive, a release agent such as a silicone resin and a paper or film backing layer.
  • a release liner comprising the pressure sensitive adhesive, a release agent such as a silicone resin and a paper or film backing layer.
  • the laminate so formed is then typically slit longitudinally into strips and the strips wound up on spools, which are stored and/or sold, as desired.
  • the laminate strip after unwinding from the spool is fed to a printer/die cutter.
  • This machine ink prints the desired graphics on the coextrudate layer and immediately cuts this layer plus attached adhesive into individual labels.
  • a small strip of the coextrudate layer is typically left between adjacent labels so that the coextrudate layer after cutting is composed of a plurality of individual, discrete labels plus an intergral matrix of coextrudate material surrounding the individual labels.
  • This matrix is then removed leaving a strip comprising a continuous paper backing layer carrying discrete, physically separated labels thereon, each label comprising an ink-printed coextrudate with attached pressure sensitive adhesive mounted on the backing layer via a silicone release agent.
  • This strip is then fed to an automatic label applying machine which manipulates the strip, for example, by sliding or rolling the strip around a peel plate at high speed, to cause the individual labels to automatically detach from the backing strip and be projected onto suitably placed bottles.
  • the procedure is similar, except that the coextruded web or sheet is not laminated to a release layer. Rather, the web or sheet, after optional winding up into bulk rolls for storage, is slit and subjected to printing/die cutting with the individual labels produced thereby being bundled together in a stack. The blow-molder then loads individual labels from the stack into the label magazine of his blow-molding machine for automatic incorporation into the blow molded bottles as part of the bottle forming operation.
  • the hot-stretched coextrudates produced as described above can also be annealed or "heat set" in accordance with known techniques. Typically, this is done after extrusion and initial chilling of the extrudate by reheating the extrudate to an elevated temperature, for example, 300°F.
  • the coextrudates can be directly processed into labels. More typically, however, the coextrudates are taken up (i.e. wound around) suitable cores to form rolls of material typically containing 500 to 15,000, preferably 2,000 to 10,000, linear meters of material in the form of continuous sheets or webs. Such rolls, which can be subdivided radially (i.e., cut in planes perpendicular to their axes to form rolls of smaller axial width) or left as is, can be stored, shipped and sold for use as needed.
  • the coextrudates of the present invention can be formed from any materials commonly employed for making coextrudate flexible plastic labels.
  • a suitable material for making the core layer for many applications in accordance with the present invention is polyethylene of low, medium or high density between 0.915 and 0.965 specific gravity. This is a relatively low cost, extrudable film-forming material whose stiffness is dependent, among other things, on the density selected and whose body and strength are sufficient for most uses. Polyethylene of lower densities, down to a specific gravity of 0.890, may be employed for greater flexibility.
  • a preferred material for the core layer is polypropylene (or a propylene copolymer) having a flex modulus ranging between about 130,000 and 300,000 psi at 73°F., depending on the stiffness desired.
  • Still other preferred materials for forming the core layer comprise copolymers of olefin monomers with ethylenically unsaturated carboxylic acid ester comonomers, such as ethylene-vinyl acetate copolymer, as well as blends of such copolymers with any and all of the other polymers and copolymers described above.
  • Still other preferred materials comprise physical blends of (1) polypropylene or copolymers of polypropylene and polyethylene and (2) ethylene-vinyl acetate (EVA) in weight ratios ranging from 50/50 to 80/20, preferably 55/45 to 65/35.
  • EVA ethylene-vinyl acetate
  • a physical blend of (1) a copolymer of polypropylene and polyethylene and (2) ethylene-vinyl acetate (EVA) is also preferred.
  • EVA ethylene-vinyl acetate
  • a preferred core layer is a physical blend of polypropylene and EVA.
  • Polystyrene is also a candidate material for the core layer particularly where a stiffer label is desired.
  • inorganic fillers may be incorporated into the polymer forming the layer.
  • Useful fillers include calcium carbonate, titanium dioxide and blends thereof. Pigments and dyes can also be added for imparting color thereto.
  • materials found suitable for the skin layers of the inventive labels are materials which are formed predominantly from polyolefins.
  • predominantly from polyolefin is meant that the layer is formed from a homopolymer or copolymer of a polyolefin or blends of such homopolymers and/or copolymers, with the proviso that at least 50% of the polymerized monomers in the layer are polyolefins.
  • Examples of such materials are homopolymers and copolymers of ethylene and propylene such as polyethylene, polypropylene and ethylene/propylene copolymer, copolymers of olefin monomers with ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid ester comonomers such as ethylene-vinyl acetate copolymer (EVA) and blends of such homopolymers and copolymers.
  • EVA ethylene-vinyl acetate copolymer
  • the polymers, copolymers and blends described above in connection with the core layer can be used.
  • meltable film-forming substances used alone or in combination such as polyethylene methyl acrylic acid, polyethylene ethyl acrylate, polyethylene methyl acrylate, acrylonitrile butadiene styrene polymer, polyethylene vinyl alcohol, nylon, polybutylene, polystyrene, polyurethane, polysulfone, polyvinylidene chloride, polypropylene, polycarbonate, polymethyl pentene, styrene maleic anhydride polymer, styrene acrylonitrile polymer, ionomers based on sodium, potassium, calcium or zinc salts of ethylene/ methacrylic acid, polymethyl methacrylates, cellulosics, fluoroplastics, polyacrylonitriles, and thermoplastic polyesters.
  • flexible plastic labels as described above are made laser-markable by including in the core layer of the label a laser-opaque material.
  • laser-opaque material is meant any material which will absorb or reflect laser light so as to cause marking of the polymer layer in which the laser-opaque material is contained.
  • the coextrudates can be made without adversely affecting the various mechanical properties such as dimensional stability, stiffness, high speed dispensability, die cutability, matrix stripability, repositionability and the like of the label product.
  • any type of laser-opaque material can be employed in accordance with the present invention.
  • the type of "interaction,” e.g., thermal degradation of the polymer, simple chemical reaction, generation of gas bubbles, etc. varies depending on the type and operation of the laser employed as well as the type of polymer material employed, and accordingly there must be a "match" of the laser-opaque material with the polymer employed as well as the type and operation of the laser employed.
  • any known laser-opaque material can be employed, so long as it "matches" both the polymer as well as the type and operation of the laser employed.
  • the preferred laser-opaque materials used in accordance with the present invention are solid, particulate materials.
  • Solid particulate materials having a high aspect ratio, particularly those which have a platelet structure, are especially preferred.
  • particulate materials it is preferable that they have an average particle size from 0.2 to 400, preferably 0.5 to 60, most preferably 1 to 25 microns.
  • Especially preferred laser-opaque materials are titanium dioxide-coated mica particles. These materials are commercially available from E. Merck Corporation of Hawthorne, New York under the designation AFFLAIR® and The Mearl Corporation of New York, New York under the designation of MEARLIN® luster pigments. These materials typically have particle sizes of 1 to 200, preferably 1 to 60, more preferably 1 to 25 microns.
  • the amount of laser-opaque material to be incorporated into the core layer of the inventive coextrudate products can vary widely. Basically, the minimum amount is that amount which is sufficient to form a visible marking of the desired intensity. The maximum amount, in turn, is usually dictated by economics, amounts over that necessary to produce a mark of a desired intensity being unnecessary. Typically, the amount will be on the order of 0.1 to 10 percent by weight, based on the weight of the material forming the core layer (including any other filler or pigment such as titanium dioxide, calcium carbonate and the like). More typically, the amount of laser-opaque material will be on the order of about 0.5 to 5 percent by weight.
  • the amount of laser opaque material in the core layer of the inventive labels in terms of effective thickness.
  • effective thickness is meant the number obtained by multiplying the thickness of the core layer, measured in mils, times the concentration of the laser-opaque material in the core layer, measured in weight percent expressed as a decimal. Measured in this way, it is preferable that the amount of laser opaque material in the core layer be enough so that the effective thickness thereof is 0.005 to 0.15, more preferably 0.01 to 0.10, even more preferably 0.02 to 0.06.
  • the labels are irradiated with laser light containing or embodying the desired information or image therein.
  • Nd/YAG systems As a practical matter, only three basic types of marking lasers are now available commercially. These are eximer lasers based on rare earth gas halides, Nd/YAG systems and pulsed carbon dioxide lasers. Of these, the Nd/YAG systems and carbon dioxide lasers are typically used for plastics. However, eximer lasers have also been used for this purpose. In accordance with the invention, each of these types of lasers can be used, although pulsed carbon dioxide TEA (transverse excited atmosphere) lasers are preferred from the point of view of cost and reliability.
  • TEA transverse excited atmosphere
  • the conditions of laser marking vary widely and are dependent on a number of factors such as the identity and amounts of laser-opaque materials in the films, film thickness and the like.
  • energy densities on the order of 0.8 to 36, preferably 1.8 to 28.8, Joules per square centimeter per pulse at pulse durations of 50 to 1,000, preferably 100 to 300, nanoseconds are appropriate.
  • the laser beam generated by the laser is passed through a suitable stencil containing the desired information to generate an information-containing laser beam.
  • This beam is then focused onto the label to be marked and the label irradiated with the laser light for the imprinting process. Exactly how this is done is well known to those skilled in the art of laser marking, and any conventional procedure for this purpose can be employed in accordance with the present invention.
  • a hot coextrudate was produced in accordance with the process described in U.S. 5,242,650 with a total thickness of 17.5 mils. The coextrudate was then hot stretched to make a film of 3.5 mils. In each example, the coextrudate was made with two identical skins, each skin layer making up 10% of the total thickness of the coextrudate and the remainder comprising the core.
  • each film was them imprinted with a simulated date and lot code by means of a Blazer 6000 Pulsed Carbon Dioxide Laser made by Lasertechnics Corporation of Albuquerque, New Mexico.
  • the laser beam produced was passed through a mask having a simulated date and lot code about one inch wide and then focused to a reduced size onto the target film to imprint the image thereon. Imprinting was done at different energy levels (3 and 4 Joules per pulse) and different reduction ratios (ratio of mask size to image size).
  • the laser beam as produced by the laser has an energy density of 0.8 Joules/cm 2 , at a maximum energy of 5 Joules.
  • the energy density of the beam as it strikes the target can be reduced from this value by reducing the energy of the laser or increased by reducing (narrowing) the beam size between the mask and the surface of the target.
  • the approximate energy densities of the laser beam striking the targets were as follows: Pulse Energy Reduction Ratio Energy Density 4 Joules 2.75:1 5 Joules/cm 2 4 Joules 2.0:1 3 Joules/cm 2 3 Joules 2.75:1 4 Joules/cm 2 3 Joules 2.0:1 2 Joules/cm 2
  • the laser produces silvery-gray laser imprinted marks.
  • the images so produced were visually observed and rated using an arbitrary scale of from 0 (no mark) to 10 (black and very distinct).
  • a coextrudate having the following composition was produced: Weight % Printing Polypropylene homopolymer (HPP) 50 Skin Ethylene-vinyl acetate copolymer (EVA-18% VA) 50 Core Layer Calcium particulate carbonate concentrate (40% particulate CaCO 3 in HPP) 40 Ethylene-vinyl acetate copolymer (EVA-18% VA) 35 Titanium dioxide concentrate (50% Rutile TiO 2 in HPP) 15 AFFLAIR 110 concentrate (20% TiO 2 coated mica in HPP) 10 Bonding Polypropylene homopolymer (HPP) 50 Skin Ethylene-vinyl acetate copolymer (EVA-18% VA) 50 The results are obtained by laser-imprinting their coextrudate in the manner described above.
  • Table 2 shows that the laser marking technique as described above produced images having a fairly high degree of contrast or intensity under essentially all the conditions tried in the experiment. This shows that images of good intensity can be produced in accordance with the present invention, even though the laser-opaque material is buried in the core and not present in the skin layers.
  • Example 1 was repeated except that initial film thickness was 15 mils before stretching and final fill thickness was 3 mils after stretching.
  • the amount of laser-opaque material in the core was varied from 0 to 3.8 weight percent, based on the weight of the core, to illustrate the effect of varying concentration of this material.
  • the specific compositions of the different layers used in these examples is set forth in the following Table 3.
  • Example 1 Printing Polypropylene homopolymer 40 Skin Ethylene-vinyl acetate copolymer (EVA) 50 Polypropylene-maleic anhydride graft copolymer (0.25 weight % maleic anhydride) 10 Core Layer Propylene-ethylene random copolymer 40 (3.2 weight % ethylene) 35-X Ethylene-vinyl acetate copolymer (EVA) 20 Titanium dioxide concentrate 5 (50% TiO 2 /50% polypropylene) Polypropylene-maleic anhydride graft copolymer AFFLAIR 110 concentrate (40% in EVA) X Bonding Polypropylene homopolymer 40 Skin Ethylene-vinyl acetate copolymer 50 Polypropylene-maleic anhydride graft polymer 10 The following results were obtained: Example AFFLAIR Concentration i.e., Amount of EVA +AFFLAIR 110° Concentration
  • Example 1 was repeated except that the coextrudates in Examples 7 and 8 had the composition set forth in the following Tables 5 and 6: Printing Polypropylene homopolymer (HPP) 40 Skin Ethylene-vinyl acetate copolymer (EVA) 50 Polypropylene-maleic anhydride graft copolymer 10 Core Layer Propylene-ethylene copolymer 35 Ethylene-vinyl acetate copolymer (EVA) 35 Titanium dioxide concentrate 20 Polypropylene-maleic anhydride graft copolymer 5 AFFLAIR 110 concentrate (20% in EVA) 5 Bonding Polypropylene homopolymer 40 Skin Ethylene-vinyl acetate copolymer 50 Polypropylene-maleic anhydride graft polymer 10 Printing AFFLAIR 110 concentrate (20% in HPP) 40 Skin Ethylene-vinyl acetate copolymer (EVA) 50 Polypropylene-maleic anhydride graft copolymer 10 Bonding
  • Example 9 a single layer extrudate was used, this single layer having the same composition as the core layer of Example 7 and the same overall thickness as the total extrudate thickness of Example 7.
  • Example Relative Thickness of Layer Containing Afflair (3 mils total) Concentration of AFFLAIR 110 in Active Layer (wt %) AFFLAIR Effective Thickness Visual Intensity of Image at Differing Energy Intensities and Reduction Ratios 3 Joules 4 Joules RR RR RR 2:1 2.75:1 2:1 2.75:1 7 80% 1.0 .024 3 3 4 4+ 8 10% 8.0 .024 ⁇ 1 Holes ⁇ 1 Holes 9 100% 1.0 .030 3 3 4 4+
  • Examples 7 and 8 compare the effect of placing the laser-opaque material in the core rather than in the skin.
  • the calculations of effective thickness in Example 8 assume that only the outer skin layer is effected by the laser impregnation. In other words, in assessing the visual impact of a laser impregnation, any effect on the lower skin layer is disregarded.
  • Example 7 shows that when the laser-opaque material is present in the core layer at an effective thickness of 0.024, visual images having significant contrast are produced at all operating conditions.
  • the same amount of laser-opaque material as used in the core of Example 7 is placed in the printing skin of the Example 8 composite, images with little if any contrast are produced at reduction ratios of 2:1, while holes are produced in the printing skin at the higher reduction ratio of 2.75:1.
  • This shows that the images produced by laser marking are not simply a result of the amount of laser opaque material in the system but also depend on where it is located.
  • this also shows that locating the laser opaque material in the core, rather than in the skin layer which first receives the laser light impinging on the article provides a significantly, and unexpectedly, superior result.
  • Example 9 was conducted.
  • a single layer extrudate having the same thickness as the coextrudates of Examples 7 and 8 was filled with the same concentration of laser opaque material as in the core of the Example 7 coextrudate.
  • the Example 9 extrudate contained a significantly greater overall amount of laser-opaque material than the coextrudate of Example 7. Notwithstanding this greater amount of active ingredient, the images produced in the Example 9 coextrudate have essentially the same visual impact as those of the Example 7 coextrudate.
  • Example 7 shows that the results obtained in Example 7 are almost identical to those obtained in Example 4 in which the coextrudate had an effective thickness of laser-opaque material of 0.023. This, in turn, shows that "effective thickness" is a meaningful number.
  • Examples 2 to 6 were repeated except that the Afflair additive was Afflair 100, rather than Afflair 110.
  • Afflair 100 is slightly larger in particle size, and as can be seen below appears to be slightly less effective.
  • Example 14 a single layer extrudate was produced rather than a multi-layer extrudate, while in one of these examples, Example 14, the extrudate was not oriented after extrusion but was simply produced as cast.
  • Example 11 Comparison of Examples 10 and 11 in the above Table 8 shows that providing an extrudate with protective skins as accomplished in accordance with the present invention, does not hurt and also may even prevent burn through at more intense conditions.
  • the composite of Example 11 is essentially the same as Example 10 in terms of the active thickness and active ingredient concentration, the only difference between that in Example 11, protective skins having no laser-opaque material therein are provided. This is significant in that it shows the coextrudated skins can be fine tuned to meet performance criteria without reducing laser-markability at the same additive cost.
  • Example 12 in which a single layer extrudate thicker than that of Example 10 and hence having more overall laser-opaque material than in Examples 10 or 11 (0.027 effective thickness rather than 0.0252) shows that the visual impact of this extrudate is no better than that of the coextrudate of Example 11 even though the extrudate of Example 12 has more laser-opaque material.
  • Examples 13 and 14 are comparable in that both have the same effective thickness of laser-opaque material.
  • the Example 14 product which is a single layer extrudate not subjected to orientation, provides a visual impact which is noticeably less intense than that provided by the Example 13 product which is composed of multiple layers having been oriented in the machine direction. This shows that the combination of burying the laser-opaque material in the core and orienting in at least the machine direction facilitates reduction in the amount of expensive laser-opaque material necessary to produce a visually acceptable image.
  • Example 2 The procedure of Examples 2 to 7 was repeated except that the thickness of the coextrudate passing out of the extrusion die was 12.5 mils and the coextrudate so made was stretched to a final product thickness of 2.5 mils. Also, the composition of the individual layers of the coextrudate was changed so that the coextrudate product was a slightly hazy, essentially transparent film.
  • compositions of the individual layers of the coextrudate are set forth in the following Table 9: Printing Polypropylene homopolymer 40 Skin Ethylene-vinyl acetate copolymer (EVA) 50 Polypropylene-maleic anhydride graft copolymer 10 Core Layer Propylene-ethylene copolymer 60 Ethylene-vinyl acetate copolymer (EVA) 32.5 Polypropylene-maleic anhydride graft copolymer 5 AFFLAIR 110 concentrate (40% in EVA) 2.5 Bonding Polypropylene homopolymer 40 Skin Ethylene-vinyl acetate copolymer (EVA) 50 Polypropylene-maleic anhydride graft copolymer 10
  • the recipe for an opaque white flexible film with a print layer, and an adhesive layer is as follows: Top Polypropylene homopolymer 50 Ethylene-vinyl acetate copolymer (EVA) 50 Central Propylene-ethylene copolymer 70 Ethylene-vinyl acetate copolymer (EVA) 10 Titanium dioxide concentrate 15 AFFLAIR 110 concentrate (16% in EVA) 5 Bottom Low-density polyethylene (LDPE) 24 Ethylene-vinyl acetate copolymer (EVA) 40 Anti-block concentrate (20% in polyethylene) 36
  • the above film was coextruded as in previous Examples 2 through 7, but the coextrudate thickness was 20 mils, and stretching was done to produce a film of 4.0 mils.
  • Example Concentration of AFFLAIR 110 in Active in Layer (wt %) Effective Thickness Visual Intensity of Images at Different Energy Intensities and Reduction Ratios 3 Joules 4 Joules RR RR RR RR 2:1 2.75:1 2:1 2.75:1 16 0.8 0.020 2+ 2+ 4 4

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Labeling Devices (AREA)

Claims (30)

  1. Coextrudat mit (1) einer flexiblen Bahn oder einem flexiblen Bogen aus Kunststoffmaterial oder (2) einem mit Druckfarbe bedruckbaren flexiblen Kunststoffetikett, das eine Kernschicht und wenigstens eine Außenhautschicht umfaßt, wobei die Kernschicht ein auf das Laserlicht reagierendes Laser-opakes Material in einer ausreichenden Menge enthält, um ein visuelles Bild in den Bereichen der Kernschicht zu erzeugen, welche mit dem Laserlicht bestrahlt werden, die wenigstens eine Außenhautschicht ein mit Druckfarbe darauf gedrucktes Bild annehmen und erhalten kann und wenigstens eine Außenhautschicht auch frei von dem Laser-opaken Material ist.
  2. Coextrudat nach Anspruch 1, bei dem wenigstens eine Außenhautschicht ein mit Druckfarbe darauf gedrucktes Bild hat.
  3. Coextrudat nach Anspruch 1 oder 2, bei dem die Dicke der Kernschicht wenigstens 50% der Dicke des Coextrudates ist.
  4. Coextrudat nach einem der Ansprüche 1 bis 3, bei dem die Dicke der wenigstens einen Außenhautschicht etwa 5 bis 15% der Dicke des Coextrudates beträgt.
  5. Coextrudat nach einem der Ansprüche 1 bis 4, bei dem die Kernschicht und die wenigstens eine Außenhautschicht vorherrschend aus Polyolefin gebildet sind.
  6. Coextrudat nach einem der Ansprüche 1 bis 5, bei dem das Laser-opake Material mit Titandioxid beschichteter Glimmer ist.
  7. Coextrudat nach einem der Ansprüche 1 bis 6, bei dem die effektive Dicke des Laser-opaken Materials in der Kernschicht 0,005 bis 0,15 ist.
  8. Coextrudat nach einem der Ansprüche 1 bis 7, bei dem die Kernschicht und die wenigstens eine Außenhautschicht copolymerisiertes Vinylacetat enthalten.
  9. Coextrudat nach einem der Ansprüche 1 bis 8, welches eine Außenhautschicht auf jeder Seite der Kernschicht enthält.
  10. Coextrudat nach einem der Ansprüche 1 bis 9, das nur in einer einzigen Richtung orientiert ist.
  11. Coextrudat nach einem der Ansprüche 1 bis 10, bei dem die Identität und Menge des Laser-opaken Materials in dem Kern ausreicht, so daß das visuelle Bild erzeugt wird, wenn das Etikett mit einem gepulsten Laser bestrahlt wird.
  12. Coextrudat nach einem der Ansprüche 1 bis 11, bei dem der gepulste Laser Laserlicht mit einer Impulsdauer von 50 bis 1000 Nanosekunden erzeugt und die Energiedichte dieses Laserlichtes 0,8 bis 36 Joules je Quadratzentimeter je Impuls ist.
  13. Coextrudat nach einem der Ansprüche 1 bis 12, bei dem die Menge des Laser-opaken Materials in der Kernschicht etwa 0,1 bis 10 Gew.-%, bezogen auf das Gewicht der Kernschicht, ist.
  14. Verfahren zur Erzeugung eines visuellen Bildes auf einem mit Druckfarbe bedruckbaren flexiblen Kunststoffetiketts, wobei das Etikett ein Coextrudat einer Kernschicht und wenigstens einer Außenhautschicht umfaßt, die Kernschicht ein Laser-opakes Material darin enthält und die Außenhautschicht frei von Laser-opakem Material ist und außerdem ein mit Druckfarbe gedrucktes Bild darauf annehmen und behalten kann, wobei das Verfahren ein Bestrahlen des Coextrudates mit Laserlicht in der Form dieses Bildes umfaßt, um das visuelle Bild dazu zu bringen, sich in der Kernschicht auszubilden.
  15. Verfahren nach Anspruch 14, bei dem die wenigstens eine Außenhautschicht ein mit Druckfarbe gedrucktes Bild darauf hat.
  16. Verfahren nach Anspruch 14 oder 15, bei dem die Dicke der Kernschicht wenigstens 50% der Dicke des Coextrudates beträgt.
  17. Verfahren nach einem der Ansprüche 14 bis 16, bei dem die Dicke der wenigstens einen Außenhautschicht etwa 5 bis 15% der Dicke des Coextrudates beträgt.
  18. Verfahren nach einem der Ansprüche 14 bis 17, bei dem die Kernschicht und die wenigstens eine Außenhautschicht vorherrschend von Polyolefin gebildet sind.
  19. Verfahren nach einem der Ansprüche 14 bis 18, bei dem das Laser-opake Material mit Titandioxid beschichteter Glimmer ist.
  20. Verfahren nach Anspruch 19, bei dem die Teilchengröße des Laser-opaken Materials 0,5 bis 200 Mikron beträgt.
  21. Verfahren nach einem der Ansprüche 14 bis 20, bei dem die effektive Dicke des Laser-opaken Materials in der Kernschicht 0,005 bis 0,15 ist.
  22. Verfahren nach einem der Ansprüche 14 bis 21, bei dem die Kernschicht und die wenigstens eine Außenhautschicht copolymerisiertes Vinylacetat enthalten.
  23. Verfahren nach einem der Ansprüche 14 bis 22, bei dem das Coextrudat eine Außenhautschicht auf jeder Seite der Kernschicht enthält.
  24. Verfahren nach einem der Ansprüche 14 bis 23, bei dem die Identität und Menge des Laser-opaken Materials in dem Kern ausreichend ist, damit sich das visuelle Bild erst bildet, wenn das Etikett mit einem gepulsten Laser bestrahlt wird.
  25. Verfahren nach einem der Ansprüche 14 bis 24, bei dem der gepulste Laser Laserlicht mit einer Impulsdauer von 50 bis 1000 Nanosekunden erzeugt und die Energiedichte dieses Laserlichtes 0,8 bis 36 Joules je Quadratzentimeter je Impuls beträgt.
  26. Verfahren nach einem der Ansprüche 14 bis 25, bei dem die Menge des Laser-opaken Materials in der Kernschicht etwa 0,1 bis 10 Gew.-%, bezogen auf das Gewicht der Kernschicht, beträgt.
  27. Kombination einer flexiblen Kunststoff-Flasche mit einem Etikett aus dem Coextrudat nach einem der Ansprüche 1 bis 13, das einstückig an der Flasche befestigt ist.
  28. Kombination nach Anspruch 27, bei der das Etikett an der Flasche mit Hilfe eines druckempfindlichen Klebstoffes oder eines hitzeaktivierbaren Klebstoffes befestigt ist.
  29. Verfahren zur Befestigung eines aus dem Coextrudat nach einem der Ansprüche 1 bis 13 gebildeten Etiketts auf einer flexiblen Kunststoff-Flasche, wobei das Etikett einstückig an der Flasche befestigt wird und sich mit der Flasche biegen kann ohne sich zu lösen, das Etikett ein mit Druckfarbe gedrucktes Bild sowie ein durch Laser erzeugtes Bild trägt, wobei dieses Verfahren umfaßt, daß man das Etikett an der Flasche befestigt, nachdem das mit Druckfarbe gedruckte Bild auf das Etikett aufgebracht ist, und danach das mit Laser erzeugte Bild auf dem Etikett durch Bestrahlen des Etiketts mit Laserlicht, welches das mit Laser erzeugte Bild verkörpert, markiert.
  30. Materialrolle mit dem Coextrudat nach einem der Ansprüche 1 bis 13 in der Form einer kontinuierlichen Bogenbahn mit einer Länge von wenigstens 500 Meter, wobei diese Bahn oder dieser Bogen unter Bildung der Rolle um sich selbst gewickelt ist.
EP95922091A 1994-06-13 1995-06-06 Lasermarkierbare plastiketiketten Expired - Lifetime EP0766546B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US259301 1981-04-29
US25930194A 1994-06-13 1994-06-13
PCT/US1995/006258 WO1995034263A1 (en) 1994-06-13 1995-06-06 Laser-markable plastic labels

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EP0766546A1 EP0766546A1 (de) 1997-04-09
EP0766546A4 EP0766546A4 (de) 1997-09-03
EP0766546B1 true EP0766546B1 (de) 2001-05-23

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EP (1) EP0766546B1 (de)
AT (1) ATE201318T1 (de)
AU (1) AU709752B2 (de)
BR (1) BR9508699A (de)
CA (1) CA2192850A1 (de)
DE (1) DE69521045T2 (de)
ES (1) ES2157329T3 (de)
WO (1) WO1995034263A1 (de)

Cited By (3)

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US7485403B2 (en) 2001-03-16 2009-02-03 Datalase Ltd. Laser-markable compositions
US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
EP3664987B1 (de) * 2017-08-11 2022-08-24 Husky Injection Molding Systems Ltd. Geformter gegenstand, behälter und verfahren zum drucken darauf

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DE19509505C1 (de) * 1995-03-16 1996-01-25 Beiersdorf Ag Mehrschichtiges Etikett
FR2762425B1 (fr) 1997-04-18 1999-06-04 Chevillot Sa Procede de marquage infalsifiable, indelebile et contraste d'objets et notamment etiquettes
US6054006A (en) * 1997-12-01 2000-04-25 Great Pacific Enterprises, Inc., Through Its Division, Montebello Packaging Method and apparatus for applying a printed label to a metal container and the labeled container produced thereby
DE19913323B4 (de) * 1999-03-24 2004-03-25 Cleanpack Gmbh Innovative Verpackungen Verfahren zum Herstellen von Etiketten
US6180318B1 (en) 1999-05-19 2001-01-30 3M Innovative Properties Company Method of imaging an article
FR2833518B1 (fr) 2001-12-14 2004-06-25 Gemplus Card Int Support d'information marquee par laser
ZA200705619B (en) * 2005-01-10 2009-01-28 Avery Dennison Corp Removable curl labels
US9422465B2 (en) 2006-11-02 2016-08-23 Avery Dennison Corporation Emulsion adhesive for washable film
AT507507A1 (de) * 2008-11-03 2010-05-15 Teich Ag Platine
US8647721B2 (en) 2008-11-05 2014-02-11 Exatec, Llc Part marking of coated plastic substrates
DE202009002784U1 (de) 2009-02-27 2009-05-20 Dittrich, Alwin Beschriftetes flächenhaftes Material und Beschriftungsvorrichtung
ES2622956T3 (es) 2009-03-30 2017-07-10 Avery Dennison Corporation Etiqueta adhesiva retirable que contiene una capa de película polimérica que tiene afinidad por el agua
BRPI1013652B1 (pt) 2009-03-30 2019-05-07 Avery Dennison Corporation Rótulo adesivo removível contendo camada de película polimérica com módulo de tração alto
PL2414473T3 (pl) 2009-03-30 2015-05-29 Avery Dennison Corp Usuwalna przylepna etykieta zawierająca naturalnie kurczliwą folię polimeryczną
EP2473357B1 (de) * 2009-08-31 2019-04-24 3M Innovative Properties Company Lasermarkierungsverfahren und artikel
JP6951972B2 (ja) 2014-10-22 2021-10-20 スリーエム イノベイティブ プロパティズ カンパニー プリント部材及びその製造方法

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FR2580233B1 (fr) * 1985-04-12 1988-11-25 Rhone Alpes Projets Plast Procede pour rendre une matiere plastique sensible au rayon laser et permettre son marquage au laser et article obtenu notamment pour le marquage des animaux

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Publication number Priority date Publication date Assignee Title
US7485403B2 (en) 2001-03-16 2009-02-03 Datalase Ltd. Laser-markable compositions
US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
US8753791B2 (en) 2001-03-16 2014-06-17 Datalase Ltd. Laser-markable compositions
US8936901B2 (en) 2001-03-16 2015-01-20 Datalase Ltd. Laser-markable compositions
EP3664987B1 (de) * 2017-08-11 2022-08-24 Husky Injection Molding Systems Ltd. Geformter gegenstand, behälter und verfahren zum drucken darauf

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BR9508699A (pt) 1997-08-12
AU709752B2 (en) 1999-09-09
WO1995034263A1 (en) 1995-12-21
EP0766546A1 (de) 1997-04-09
AU2690195A (en) 1996-01-05
ATE201318T1 (de) 2001-06-15
DE69521045T2 (de) 2001-09-06
ES2157329T3 (es) 2001-08-16
CA2192850A1 (en) 1995-12-21
EP0766546A4 (de) 1997-09-03
DE69521045D1 (de) 2001-06-28

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