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WO2000013887A1 - Structures composites multicouches - Google Patents

Structures composites multicouches Download PDF

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Publication number
WO2000013887A1
WO2000013887A1 PCT/US1999/020458 US9920458W WO0013887A1 WO 2000013887 A1 WO2000013887 A1 WO 2000013887A1 US 9920458 W US9920458 W US 9920458W WO 0013887 A1 WO0013887 A1 WO 0013887A1
Authority
WO
WIPO (PCT)
Prior art keywords
construction
layer
adhesive
substrate
films
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
Application number
PCT/US1999/020458
Other languages
English (en)
Inventor
Karl Josephy
Ronald Ugolick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avery Dennison Corp
Original Assignee
Avery Dennison Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Avery Dennison Corp filed Critical Avery Dennison Corp
Priority to AU58134/99A priority Critical patent/AU5813499A/en
Publication of WO2000013887A1 publication Critical patent/WO2000013887A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • 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
    • G09F2003/0257—Multilayer

Definitions

  • the present invention relates to multilayer constructions used for making tags, labels and the like and, more particularly, to thin highly- conformable, cost efficient coextruded pressure-sensitive adhesive constructions.
  • PSA label constructions such as labels, tapes, decals and the like are known in the art.
  • PSA label constructions are commonly used to apply a particular facestock having a specific nature of printing to an object or article.
  • PSA label constructions typically comprise a release liner, a PSA layer disposed onto the liner, and a facestock laminated onto the PSA layer. This lamination may be formed by first coating or laminating the PSA to the liner, then laminating the facestock onto the PSA-coated liner; or alternatively by coating or laminating the PSA to the facestock, then the PSA-coated facestock onto the liner.
  • the facestock is characteristically made from a web or sheet of paper, cardboard or plastic, which is printed on with information or other indicia either before or after it is laminated to the PSA and liner.
  • a plastic facestock can be a single layer of a single material or multiple layers of plastics formed either by lamination or coextrusion.
  • the laminate is printed on the exposed facestock surface, die-cut down to the liner surface to outline the label shape, and the waste material between the labels (matrix) is stripped out.
  • the PSA label facestock and adhesive is then adhered to a substrate surface by separating the label from the liner and causing the PSA layer of the label to come into contact and bond with the substrate surface with the PSA layer providing the bonding force (as measured by a peel test).
  • the label is separated from the liner by bending the liner back over a peel plate, whereupon the label is sufficiently stiff to cause the label to continue on a straight path toward the desired substrate surface.
  • This peel plate dispensing generally is done at room temperature.
  • separation refers to removal of the label from the liner
  • application refers to adhesion of the label to the substrate surface
  • dispenser refers to the combined steps of separation and application.
  • Peel plate dispensing denotes the use of a peel plate in the separation of liner from label.
  • the layer thicknesses and layer materials for such conventional PSA constructions must also be selected to provide desired properties of convertibility, e.g., by conventional converting techniques such as by die-cutting and matrix-stripping; dispensability, e.g., by conventional dispensing equipment such as by peel plate; and conformability, e.g., enabling the applied label to adhere to an irregular or deformable substrate surface without becoming detached or damaged.
  • the stiffness of a PSA construction will have an impact on its convertibility and dispensability.
  • the stiffness of a label of a given material decreases as the label is made thinner.
  • the conformability of a PSA construction is known to decrease as the construction stiffness is increased.
  • the objective stiffness for a PSA construction is a compromise between convertibility/dispensability and conformability (and cost) . Too low a stiffness of the label will cause the label to go around the peel plate with the liner. It is one objective of this invention to provide a minimal material label construction with enough stiffness to be dispensable using a peel plate.
  • the present invention utilizes a unique distribution of polymeric facestock material and, optionally, adhesive material, through the thickness of the construction which results in an increase in the stiffness of the facestock and allows the use of less label material.
  • the label has sufficient stiffness to be peel-plate dispensable.
  • the present invention also relates to a unique method of label dispensing which allows the further reduction of material used in label construction while maintaining sufficient stiffness to be peel-plate dispensable.
  • Another aspect of the invention is a method of peel plate dispensing where at least the leading edge of the label is maintained at a temperature of at least about 5°C below room temperature.
  • the invention relates to a die-cuttable, and matrix-strippable adhesive composite construction which comprises A. a composite facestock which comprises first and second continuous polymeric films, each having an upper surface and a lower surface, and each independently having a thickness of from about 0.1 to about 2 mils, said first and second films being separated by a continuous layer of material (separation layer) having a Young's Modulus less than the Young's Modulus of the first and second polymeric films, and
  • a substrate adhesive layer having an upper surface and a lower surface wherein the upper surface of the substrate adhesive layer is adhesively joined to the lower surface of the second film.
  • the separation layer in A is a layer of adhesive which may be a PSA.
  • the separation layer and/or the second polymeric film contribute to the peel of the PSA construction thereby reducing the amount of substrate adhesive required to meet the bonding criteria when bonded to an application substrate.
  • the second polymeric film layer (the layer closet to the substrate adhesive layer) comprise a polymer having a glass transition temperature (Tg) as measured by DSC, of between about 10°C and 30°C.
  • Tg glass transition temperature
  • the total thickness of the two polymer films and the separation layer is between about 0.2 to 3.5 mils.
  • the invention in another embodiment, relates to a multilayer composite construction which comprises: (A) a separation layer of polymeric film material having an upper surface and a lower surface,
  • each of said first and second stiffening layers comprises a polymeric film material having a Young's Modulus that is greater than the Young's modulus of the separation layer and the skin layer on either side of the stiffening layer.
  • This composite may be combined with an adhesive layer and a release liner to form labelstock which is die-cuttable and matrix-strippable.
  • Die-cut labels also are described which are prepared by die-cutting the die-cuttable and matrix-strippable adhesive constructions of the invention, particularly, those constructions described above in combination with a substrate having a release surface, wherein the release surface is in contact with a lower surface of the adhesive layer of the coextrudate.
  • the substrate having a release surface is a release coated liner or carrier.
  • Fig. 1 is a schematic side elevation one method of making a construction of the invention
  • Fig. 1 A is a cross-sectional side view of an adhesive construction of the invention as prepared in Fig. 1 .
  • Fig. 1 B is a cross-sectional side view of an adhesive construction of the invention as prepared in Fig. 1 with a release liner.
  • Fig. 2 is a schematic of another method of making an adhesive construction of the invention.
  • Fig. 2A is a cross-sectional side view of a construction of the invention as prepared in Fig. 2.
  • Fig. 2B is a cross-sectional side view of a construction of the invention as prepared in Fig. 2 with an adhesive layer and release liner.
  • the invention relates to a die-cuttable, matrix-strippable, adhesive composite construction which comprises
  • A a composite facestock which comprises first and second continuous polymeric films, each having an upper surface and a lower surface, and each independently having a thickness of from about 0.1 to about 2 mils, said first and second films being separated by a continuous layer of material (hereinafter sometimes referred to as the separation layer) having a Young's Modulus less than the Young's Modulus of the first and second polymeric films, and
  • the second polymeric film and/or the separation layer (e.g., an internal adhesive) of these constructions contribute to the peel force required to separate the facestock from an application substrate. Accordingly, the amount of substrate adhesive normally used can be reduced in these constructions without sacrificing bonding strength.
  • the continuous layer of material used to separate the two polymeric film layers in this embodiment and having a lower Young's Modulus than the adjacent first and second polymer films can comprise any number of materials such as, for example, polymeric films, thin foam materials, and interior adhesives such as pressure sensitive adhesives.
  • the total thickness of the two polymer films and the separation layer is between about 0.2 to about 3 mils, more preferably from about 0.2 to about
  • the thickness of the separation layer may generally range from about 0.02 to about 2 mils, and more often will be from about 0.02 to about 1 .0 mil.
  • One preferred separation layer is a continuous layer of adhesive such as the pressure sensitive adhesives described below.
  • the PSA does not have to have all of the properties of a standard PSA.
  • the interior PSA needs to have only enough tack to adhere to the film on either side.
  • the use of an interior adhesive layer also appears to contribute to the adhesive properties of the overall constructions of the invention.
  • the continuous polymeric films can comprise a polyolefin or olefin blend which elongates under the use conditions and contributes to the adhesive properties, particularly when the continuous polymeric film deforms under peel conditions.
  • the composite constructions comprise
  • first skin layer of polymeric material having an ink printable upper surface and a lower surface
  • second skin layer of polymeric material having an upper surface and a lower surface
  • D a first stiffening layer between and joined to the upper surface of the separation layer and the lower surface of the first skin layer
  • each of said first and second stiffening layers comprises a polymeric film material having a Young's Modulus that is greater than the Young's Modulus of the separation layer and the skin layer on either side of the stiffening layer.
  • the ratios of the thicknesses of the first skin/first stiffening/separation/second stiffening/second skin layers may vary over a wide range although the separation layer generally is the thickest layer. Ratios ranging from 1 /1 /96/1 /1 to
  • 1 5/5/60/5/1 5 are useful.
  • a particularly preferred ratio is 1 0/5/70/5/1 0.
  • the multilayer composite constructions of the invention may comprise more than the three or five layers described above.
  • the multilayer structures may be represented by A(BC)x structures where A and C represent the first and second films, respectively, B is a separation layer as described above, and x is at least 1 .
  • Layers A and C may be of the same or different material, the thicknesses of the layers may be the same or different, and x may be a number as high as 1 00 or 300 or higher.
  • the multilayer composite constructions may be prepared by a variety of techniques such as by sequential coating and formation of the individual layers, triple die coating, extension coating or multiple layers onto adhesives, etc.
  • One preferred method for preparing the multilayer composite constructions of this embodiment is by coextrusion of the layers.
  • the composite construction is a balance coextrudate. This is particularly preferred to control curl.
  • a balanced coextrusion occurs when the first and second skins as well as the first and second stiffening layers are similar or equivalent in terms of thickness and material.
  • the composites exhibit higher stiffnesses than similar composites where the stiffening layers are omitted or when the stiffening material is present as a single unseparated layer.
  • the composites generally are formed by coextrusion of the five layers of polymer material, and the composites may be combined with an adhesive layer and a release liner to form label stock which is die-cuttable, matrix-strippable and has sufficient stiffness to be dispensed over a peel-plate.
  • the first and second polymeric films of the composite constructions can be obtained from any polymeric material that is capable of being extruded, and particularly polymeric materials that can be coextruded with a variety of adhesives, and more particularly, as described below, with pressure sensitive adhesives.
  • the polymeric film material may have a solubility parameter that is inconsistent with or incompatible with that of the adhesive to prevent migration between the two layers when coextruded.
  • the construction of the first embodiment can be prepared by other processes known to those skilled in the art.
  • the composites can be formed by applying an adhesive layer to a release surfaces of a removable substrate and sequentially deposition a layer of film-forming material, a second layer of adhesive (internal adhesive) and a second layer of film forming material.
  • the various polymeric and adhesive materials can be applied to the surface of the first adhesive layer in the form of a hot melt, aqueous dispersion or solution by roll, spray, electrostatic, die or extrusion processes.
  • the polymeric film material also should, when combined with the adhesive layer, provide a sufficiently self-supporting construction to facilitate label dispensing (label separation and application.)
  • the polymeric film material is chosen to provide the construction with the desired properties such as printability, die-cuttability, matrix-strippability, dispensability, etc.
  • the composite facestock of the invention can be uniaxially or biaxially oriented (e.g., by heat stretching and heat setting) to improve the properties of the facestock. Orientation in the machine direction will increase machine direction stiffness and improve dispensability. Machine direction or biaxial orientation of the composite facestocks can be accomplished by techniques well known in the art. Stretch ratios of from about 2: 1 to 1 0: 1 are useful, and a stretch ratio in the range of about 4: 1 to 9: 1 is preferred. A most preferred range is from about 5: 1 to 8: 1 .
  • the polymeric film materials useful in the composites of the first and second embodiments of the present invention include polystyrenes, polyolefins, polyamides, polyesters, polycarbonates, polyvinyl alcohol, poly(ethylene vinyl alcohol), polyurethanes, polyacrylates, poly(vinyl acetates), ionomers and mixtures thereof.
  • the polymeric film material is a blend of a major amount of a polyolefin. Typically, the blends contain greater than 55%, or greater than 70% by weight polyolefin.
  • the polyolefins may be blended with one or more of the polymers listed previously.
  • a preferred blend is the blend of a polyolefin and a poly(vinyl) acetate such as ethylene vinyl acetate.
  • the polymeric film material is a polyolefin.
  • the polyolefin film materials generally are characterized as having a melt index or melt flow rate of less than 30, more often less than 20, and most often less than 10 as determined by ASTM Test Method 1 238.
  • the polyolefins which can be utilized as the polymeric film material include polymers and copolymers of ethylene, propylene, 1 -butene, etc., or blends of mixtures of such polymers and copolymers.
  • the polyolefins comprise polymers and copolymers of ethylene and propylene.
  • the polyolefins comprise propylene homopolymers, and copolymers such as propylene-ethylene and propylene-1 -butene copolymers. Blends of polypropylene and polyethylene with each other, or blends of either or both of them with polypropylene-polyethylene copolymer also are useful.
  • the polyolefin film materials are those with a very high propylenic content, either polypropylene homopolymer or propylene-ethylene copolymers or blends of polypropylene and polyethylene with low ethylene content, or propylene-1 -butene copolymers or blend of polypropylene and poly- 1 -butene with low butene content.
  • polyethylenes can be utilized as the polymeric film material including low, medium, and high density polyethylenes.
  • LDPE low density polyethylene
  • the propylene homopolymers which can be utilized as the polymeric film material in the constructions of the invention, either alone, or in combination with a propylene copolymer as described herein, include a variety of propylene homopolymers such as those having melt flow rates (MFR) from about 0.5 to about 20 as determined by ASTM Test D 1 238, condition L.
  • MFR melt flow rates
  • propylene homopolymers having MFR's of less than 1 0, and more often from about 4 to about 1 0 are particularly useful and provide facestocks having improved die-cuttability.
  • Useful propylene homopolymers also may be characterized as having densities in the range of from about 0.88 to about 0.92 g/cm 3 .
  • a number of useful propylene homopolymers are available commercially from a variety of sources, and some useful polymers include: 5A97, available from Union Carbide and having a melt flow of 1 2.0 g/1 0 min and a density of 0.90 g/cm 3 ; DX5E66, also available from Union Carbide and having an MFI of 8.8 g/1 0 min and a density of 0.90 g/cm 3 ; and WRD5-1 057 from Union Carbide having an MFI of 3.9 g/10 min and a density of 0.90 g/cm 3 .
  • Useful commercial propylene homopolymers are also available from Fina and Montel.
  • the propylene copolymers generally comprise copolymers of propylene and up to 1 0% or even 20% by weight of at least one other alpha olefin such as ethylene, 1 -butene, 1 -pentene, etc.
  • the propylene copolymers are propylene-ethylene copolymers with ethylenic contents with from about 0.2% to about 1 0% by weight.
  • Such copolymers are prepared by techniques well known to those skilled in the art, and these copolymers are available commercially from, for example, Union Carbide.
  • a propylene-ethylene copolymer containing about 3.2% by weight of ethylene is available from Union Carbide under the designation D56D20.
  • Another Union Carbide propylene-ethylene copolymer is D56D8, which contains 5.5% by weight of ethylene.
  • Particularly useful polyamide resins include resins available from
  • Grivory G-21 is an amorphous nylon copolymer having a glass transition temperature of 1 25 ° C, a melt flow index (DIN 53735) of 90 ml/10 min and an elongation at break (ASTM D638) of 1 5.
  • Grivory CF65 is a nylon 6/1 2 film grade resin having a melting point of 1 35 ° C, a melt flow index of 50 ml/1 0 min, and an elongation at break in excess of 350%.
  • Grilon CR9 is another nylon 6/1 2 film grade resin having a melting point of 200°C, a melt flow index of 200 ml/ 1 0 min, and an elongation at break at 250% .
  • Grilon XE 3303 is a nylon 6.6/6.1 0 film grade resin having a melting point of 200°C, a melt flow index of 60 ml/ 1 0 min, and an elongation at break of 1 00%.
  • Other useful polyamide resins include those commercially available from, for example, Union Camp of Wayne, New Jersey under the Uni-Rez product line, and dimer-based polyamide resins available from Bostik, Emery, Fuller, Henkel (under the Versamid product line) .
  • Suitable polyamides include those produced by condensing dimerized vegetable acids with hexamethylene diamine.
  • Examples of polyamides available from Union Camp include Uni-Rez 2665; Uni-Rez 2620; Uni-Rez 2623; and Uni-Rez 2695.
  • Polystyrenes can also be utilized as the polymeric film material in the coextruded adhesive constructions of the invention and these include homopolymers as well as copolymers of styrene and substituted styrene such as alpha-methyl styrene.
  • styrene copolymers and terpolymers include: acrylonitrile-butene-styrene (ABS); styrene-acrylonitrile copolymers (SAN); styrene butadiene (SB); styrene-maleic anhydride (SMA); and styrene- methyl methacrylate (SMMA); etc.
  • An example of a useful styrene copolymer is KR-10 from Phillips Petroleum Co. KR-10 is believed to be a copolymer of styrene with 1 ,3-butadiene.
  • Polyurethanes also can be utilized as the polymeric film material in the coextruded adhesive constructions of the invention, and the polyurethanes may include aliphatic as well as aromatic polyurethanes.
  • Polyesters prepared from various glycols or polyols and one or more aliphatic or aromatic carboxylic acids also are useful film materials.
  • Polyethylene terephthalate (PET) and PETG (PET modified with cyclohexanedimethanol) are useful film forming materials which are available from a variety of commercial sources including Eastman.
  • Kodar 6763 is a PETG available from Eastman Chemical.
  • Selar PT-8307 is polyethylene terephthalate.
  • Acrylate polymers and copolymers and alkylene vinyl acetate resins also are useful as the film forming materials in the preparation of the coextruded adhesive constructions of the invention.
  • Commercial examples of available polymers include Escorene UL-7520 (Exxon), a copolymer of ethylene with 1 9.3% vinyl acetate; Nucrell 699 (duPont), an ethylene copolymer containing 1 1 % of methacrylic acid; etc. lonomers (polyolefins containing ionic bonding of molecular chains) also are useful.
  • ionomers examples include ionomeric ethylene copolymers such as Surlyn 1706 (duPont) which is believed to contain interchain ionic bonds based on a zinc salt of ethylene methacrylic acid copolymer. Surlyn 1 702 from duPont also is a useful ionomer.
  • Polycarbonates also are useful, and these are available from the Dow Chemical Co. (Calibre) G.E. Plastics (Lexan) and Bayer (Makrolon). Most commercial polycarbonates are obtained by the reaction of bisphenol A and carbonyl chloride in an interfacial process. Molecular weights of the typical commercial polycarbonates vary from about 22,000 to about 35,000, and the melt flow rates generally are in the range of from 4 to 22 g/1 0 min.
  • the polymeric film material may contain inorganic fillers and other organic or inorganic additives to provide desired properties such as appearance properties (opaque or colored films), durability and processing characteristics.
  • Nucleating agents can be added to increase crystallinity and thereby increase stiffness.
  • useful materials include calcium carbonate, titanium dioxide, metal particles, fibers, flame retardants, antioxidant compounds, heat stabilizers, light stabilizers, ultraviolet light stabilizers, antiblocking agents, processing aids, acid aceptors, etc.
  • nucleating agents and pigments can be incorporated into the films of the present invention.
  • the amount of nucleating agent added should be an amount sufficient to provide the desired modification of the crystal structure while not having an adverse effect on the desired properties of the films. It is generally desired to utilize a nucleating agent to modify the crystal structure and provide a large number of considerably smaller crystals or spherulites to improve the transparency (clarity), and stiffness, and the die- cuttability of the film. Obviously, the amount of nucleating agent added to the film formulation should not have a deleterious affect on the clarity of the film. Nucleating agents which have been used heretofore for polymer films include mineral nucleating agents and organic nucleating agents.
  • mineral nucleating agents examples include carbon black, silica, kaolin and talc.
  • organic nucleating agents which have been suggested as useful in polyolefin films include salts of aliphatic mono-basic or di-basic acids or aryalkyl acids such as sodium succinate, sodium glutarate, sodium caproate, sodium 4- methylvalerate, aluminum phenyl acetate, and sodium cinnamate.
  • Alkali metal and aluminum salts of aromatic and alicyclic carboxylic acids such as aluminum benzoate, sodium or potassium benzoate, sodium betanaphtholate, lithium benzoate and aluminum tertiary-butyl benzoate also are useful organic nucleating agents.
  • Substituted sorbitol derivatives such as bis (benzylidene) and bis
  • alkylbenzilidine sorbitols wherein the alkyl groups contain from about 2 to about 1 8 carbon atoms are useful nucleating agents. More particularly, sorbitol derivatives such as 1 ,3,2,4-dibenzylidene sorbitol, 1 ,3,2,4-di-para- methylbenzylidene sorbitol, and 1 ,3,2,4-di-para-methylbenzylidene sorbitol are effective nucleating agents for polypropylenes. Useful nucleating agents are commercially available from a number of sources. Millad 8C-41 -10, Millad 3988 and Millad 3905 are sorbitol nucleating agents available from Milliken Chemical Co.
  • the amounts of nucleating agent incorporated into the film formulations of the present invention are generally quite small and range from about 1 00 to about 6000 ppm of the film. Preferably the amount of nucleating agent is in the range of about 1000 to about 5000 ppm.
  • the polymeric film material for the first polymeric film (first embodiment) and the first skin layer (second embodiment) is chosen to provide a continuous polymer film in the product with the desired properties such as improved printability, weatherability, strength, water resistance, abrasion resistance, gloss, die-cuttability, and matrix strippability. It is particularly desirable that the surface of the first film and first skin layer can be printed or adapted to be printed with inks using printing techniques such as flexographic printing, screen printing, offset lithography, letter press, thermal transfer, etc., and that the applied ink has acceptable adhesion to the surface of the film of the adhesive construction.
  • the choice of polymeric film forming material also is determined by its physical properties such as melt viscosity, high speed tensile strength, percent elongation etc.
  • coextrusion of the polymeric film materials and the adhesives to form the coextrudate of the first embodiment is facilitated when the melt viscosities of the two materials, i.e., the polymeric film material of the first layer and the adhesive material, are similar.
  • the choice of polymeric film material to be utilized in the formation of the coextruded adhesive constructions of the present invention may be dependent upon the melt viscosity of the adhesive being coextruded with the polymeric film forming material.
  • the polymeric film material of the first layer preferably has a hot melt viscosity that is within a factor of from about 0.07 to about 1 5 times, more often greater than 1 to about 1 5 times, and preferably from 1 up to about 1 0 times the hot melt viscosity of the adhesive at the shear rates incurred in the coextrusion process.
  • the thicknesses of the polymer film layers are independently from about 0.1 to about 1 .5 or even 2.0 mils. More often the thicknesses of the films are from about 0.2 to about 1 .0 mil. A thickness of about 0.5 mils is particularly useful.
  • the overall thickness of the adhesive composite is from about 0.2 mil to about 2.35 mils, 2.5 mils or even 3.0 mils.
  • One preferred range of overall thickness for the adhesive composite is from about 1 to 2.4 mils, more preferably from 1 .5 to 2.4 mils.
  • the constructions of the present invention also include an adhesive layer (referred to as "substrate adhesive") having an upper surface and a lower surface wherein the upper surface of the adhesive layer is adhesively joined to the lower surface of the second polymer film in the first embodiment, and to the second skin layer of the second embodiment.
  • the constructions also contain an interior adhesive.
  • the adhesives may be a heat-activated adhesives, hot melt adhesives, or pressure sensitive adhesives (PSA). Adhesives which are tacky at any temperature up to about 1 60°C (about 320° F) are particularly useful.
  • PSAs which are tacky at ambient temperatures are particularly useful in the adhesive constructions of the present invention.
  • a variety of conventional PSAs can be utilized provided that the viscosity is or can be modified to be similar to the viscosity of the polymeric film material which is being coextruded with the adhesive.
  • Useful PSA compositions are fluid or pumpable at the temperatures used in the melt processing.
  • the adhesive compositions should not significantly degrade or gel at the temperature employed and over the time required for melt processing and extrusion.
  • the adhesive compositions have a viscosity of from 1000 poise to 1 ,000,000 poise at the processing temperature.
  • the adhesives may generally be classified into the following categories:
  • Random copolymer adhesives such as those based upon acrylate and/or methacrylate copolymers, ⁇ -olefin copolymers, silicone copolymers, chloroprene/acrylonitrile copolymers, and the like.
  • Block copolymer adhesives including those based upon linear block copolymers (i.e., A-B and A-B-A type), branched block copolymers, star block copolymers, grafted or radial block copolymers, and the like, and Natural and synthetic rubber adhesives.
  • linear block copolymers i.e., A-B and A-B-A type
  • branched block copolymers i.e., A-B and A-B-A type
  • star block copolymers grafted or radial block copolymers, and the like
  • Natural and synthetic rubber adhesives Natural and synthetic rubber adhesives.
  • PSAs including silicone-based PSAs, rubber-based PSAs, and acrylic-based PSAs are useful.
  • Another commercial example of a hot melt adhesive is H21 87-01 , sold by Ato Findley, Inc., of Wauwatusa, Wisconsin.
  • rubber based block copolymer PSAs described in U.S. Patent 3,239,478 (Harlan) also can be utilized in the coextruded adhesive constructions of the present invention, and this patent is hereby incorporated by a reference for its disclosure of such hot melt adhesives.
  • the pressure sensitive adhesives utilized in the present invention comprise rubber based elastomer materials such as linear, branched, grafted, or radial block copolymers represented by the diblock structures A-B, the triblock A-B-A, the radial or coupled structures (A- B) n , and combinations of these where A represents a hard thermoplastic phase or block which is non-rubbery or glassy or crystalline at room temperature but fluid at higher temperatures, and B represents a soft block which is rubbery or elastomeric at service or room temperature.
  • thermoplastic elastomers may comprise from about 75% to about 95% by weight of rubbery segments and from about 5% to about 25% by weight of non-rubbery segments.
  • the non-rubbery segments or hard blocks comprise polymers of mono- and polycyclic aromatic hydrocarbons, and more particularly vinyl- substituted aromatic hydrocarbons which may be monocyclic or bicyclic in nature.
  • the preferred rubbery blocks or segments are polymer blocks of homopolymers or copolymers of aliphatic conjugated dienes. Rubbery materials such as polyisoprene, polybutadiene, and styrene butadiene rubbers may be used to form the rubbery block or segment.
  • Particularly preferred rubbery segments include polydienes and saturated olefin rubbers of ethylene/butylene or ethylene/propylene copolymers. The latter rubbers may be obtained from the corresponding unsaturated polyalkylene moieties such as polybutadiene and polyisoprene by hydrogenation thereof.
  • the block copolymers of vinyl aromatic hydrocarbons and conjugated dienes which may be utilized include any of those which exhibit elastomeric properties.
  • the block copolymers may be diblock, triblock, multiblock, starblock, polyblock or graftblock copolymers. Throughout this specification and claims, the terms diblock, triblock, multiblock, polyblock, and graft or grafted-block with respect to the structural features of block copolymers are to be given their normal meaning as defined in the literature such as in the Encyclopedia of Polymer Science and Engineering, Vol. 2, ( 1 985) John Wiley &
  • Such block copolymers may contain various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up to about
  • multi-block copolymers may be utilized which are linear or radial symmetric or asymmetric and which have structures represented by the formulae A-B, A-B-A, A-B-A-B, B-A-B, (AB) 0 1 2 ...BA, etc., wherein A is a polymer block of a vinyl aromatic hydrocarbon or a conjugated diene/vinyl aromatic hydrocarbon tapered copolymer block, and B is a rubbery polymer block of a conjugated diene.
  • the block copolymers may be prepared by any of the well-known block polymerization or copolymerization procedures including sequential addition of monomer, incremental addition of monomer, or coupling techniques as illustrated in, for example, U.S. Patents 3,251 ,905; 3,390,207; 3,598,887; and 4,21 9,627.
  • tapered copolymer blocks can be incorporated in the multi-block copolymers by copolymerizing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers utilizing the difference in their copolymerization reactivity rates.
  • Various patents describe the preparation of multi-block copolymers containing tapered copolymer blocks including U.S. Patents 3,251 ,905; 3,639,521 ; and 4,208,356, the disclosures of which are hereby incorporated by reference.
  • Conjugated dienes which may be utilized to prepare the polymers and copolymers are those containing from 4 to about 1 0 carbon atoms and more generally, from 4 to 6 carbon atoms. Examples include from 1 ,3-butadiene, 2-methyl-1 ,3-butadiene (isoprene), 2, 3-dimethyl-1 ,3-butadiene, chloroprene,
  • conjugated dienes 1 ,3-pentadiene, 1 ,3-hexadiene, etc. Mixtures of these conjugated dienes also may be used.
  • the preferred conjugated dienes are isoprene and 1 ,3-butadiene.
  • vinyl aromatic hydrocarbons which may be utilized to prepare the copolymers include styrene and the various substituted styrenes such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1 ,3-dimethylsty- rene, alpha-methylstyrene, beta-methylstyrene, p-isopropylstyrene, 2,3-dimeth- ylstyrene, o-chlorostyrene, p-chlorostyrene, o-bromostyrene, 2-chloro-4-methyl- styrene, etc.
  • the preferred vinyl aromatic hydrocarbon is styrene.
  • the number average molecular weight of the block copolymers, prior to hydrogenation, is from about 20,000 to about 500,000, preferably from about 40,000 to about 300,000.
  • the average molecular weights of the individual blocks within the copolymers may vary within certain limits.
  • the vinyl aromatic block will have a number average molecular weight in the order of about 2000 to about 1 25,000, and preferably between about 4000 and 60,000.
  • the conjugated diene blocks either before or after hydrogenation will have number average molecular weights in the order of about 10,000 to about 450,000 and more preferably from about 35,000 to 1 50,000.
  • the vinyl content of the conjugated diene portion generally is from about 10% to about 80%, and the vinyl content is preferably from about 25% to about 65%, particularly 35% to 55% when it is desired that the modified block copolymer exhibit rubbery elasticity.
  • the vinyl content of the block copolymer can be measured by means of nuclear magnetic resonance.
  • diblock copolymers include styrene— butadiene (SB), styrene-isoprene (SI), and the hydrogenated derivatives thereof.
  • triblock polymers include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), alpha-methylstyrene-butadiene-alpha- methylstyrene, and alpha-methylstyrene-isoprene alpha-methylstyrene.
  • block copolymers useful as the adhesives in the present invention include those available from Shell Chemical Company and listed in the following Table II.
  • D1 320X Multi-arm (Sl) n 10/90 NA Vector 41 1 1 is a SIS block copolymer available from Dexco of Houston, Texas.
  • a styrene-ethylene-butylene styrene (SEBS) block copolymer Upon hydrogenation of the SBS copolymers comprising a rubbery segment of a mixture of 1 ,4 and 1 ,2 isomers, a styrene-ethylene-butylene styrene (SEBS) block copolymer is obtained. Similarly, hydrogenation of an SIS polymer yields a styrene-ethylene propylene-styrene (SEPS) block copolymer.
  • SEBS styrene-ethylene-butylene styrene
  • the selective hydrogenation of the block copolymers may be carried out by a variety of well known processes including hydrogenation in the presence of such catalysts as Raney nickel, noble metals such as platinum, palladium, etc., and soluble transition metal catalysts.
  • Suitable hydrogenation processes which can be used are those wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst.
  • Such procedures are described in U.S. Patents 3, 1 1 3,986 and 4,226,952, the disclosures of which are incorporated herein by reference.
  • Such hydrogenation of the block copolymers which are carried out in a manner and to extent as to produce selectively hydrogenated copolymers having a residual unsaturation content in the polydiene block of from about
  • the conjugated diene portion of the block copolymer is at least 90% saturated and more often at least 95% saturated while the vinyl aromatic portion is not significantly hydrogenated.
  • Particularly useful hydrogenated block copolymers are hydrogenated products of the block copolymers of styrene-isoprene-styrene such as a styrene-(ethylene/propyl- ene)-styrene block polymer.
  • a polystyrene-polybutadiene-polystyrene block copolymer is hydrogenated, it is desirable that the 1 ,2-polybutadiene to
  • 1 ,4-polybutadiene ratio in the polymer is from about 30:70 to about 70:30.
  • the resulting product resembles a regular copolymer block of ethylene and 1 -butene (EB).
  • EB ethylene and 1 -butene
  • the conjugated diene employed as isoprene the resulting hydrogenated product resembles a regular copolymer block of ethylene and propylene (EP) .
  • Kraton G 1 652 is a hydrogenated SBS triblock comprising about 30% by weight of styrene end blocks and a mid- block which is a copolymer of ethylene and 1 -butene (EB) .
  • a lower molecular weight version of G 1 652 is available from Shell under the designation Kraton G 1 650.
  • Kraton G 1 651 is another SEBS block copolymer which contains about 33% by weight of styrene.
  • Kraton G 1 657 is an SEBS diblock copolymer which contains about 1 3%w styrene. This styrene content is lower than the styrene content in Kraton G 1 650 and Kraton G 1 652.
  • the selectively hydrogenated block copolymer is of the formula
  • the blocks of A constituting about 5% to about 95% by weight of the copolymer; and the unsaturation of the block B is less than about 1 0% of the original unsaturation.
  • the unsaturation of block B is reduced upon hydrogenation to less than 5% of its original value, and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its original value.
  • the block copolymers may also include functionalized polymers such as may be obtained by reacting an alpha, beta-olefinically unsaturated monocarboxylic or dicarboxylic acid reagent onto selectively hydrogenated block copolymers of vinyl aromatic hydrocarbons and conjugated dienes as described above.
  • the reaction between the carboxylic acid reagent in the graft block copolymer can be effected in solutions or by a melt process in the presence of a free radical initiator.
  • Patent 4,578,429 contains an example of grafting of Kraton G 1 652 (SEBS) polymer with maleic anhydride with 2,5-dimethyl-2,5-di(t-butylperoxy) hexane by a melt reaction in a twin screw extruder. (See Col. 8, lines 40-61 .)
  • Examples of commercially available maleated selectively hydrogenated copolymers of styrene and butadiene include Kraton FG 1 901 X, FG 1 921 X, and FG 1 924X from Shell, often referred to as maleated selectively hydrogenated SEBS copolymers.
  • FG 1 901 X contains about 1 .7%w bound functionality as succinic anhydride and about 28%w of styrene.
  • FG1 921 X contains about 1 %w of bound functionality as succinic anhydride and 29%w of styrene.
  • FG 1 924X contains about 1 3% styrene and about 1 % bound functionality as succinic anhydride.
  • Useful block copolymers also are available from Nippon Zeon Co., 2-1 , Marunochi, Chiyoda-ku, Tokyo, Japan.
  • Quintac 3530 is available from Nippon Zeon and is believed to be a linear styrene-isoprene- styrene block copolymer.
  • the polymer film materials and adhesive compositions used to form the constructions of the present invention may be neat, or they may be emulsions or solvent-based.
  • Emulsion and solvent-based acrylic based PSAs are known and described in, for example, U.S. Patent No. 5,639,81 1 and 5, 1 64,444, respectively, and these patents are hereby incorporated by reference for such disclosures.
  • the water may be removed in an extruder by using the process described and claimed in U.S. Patent 5,71 6,669 (LaRose et al) .
  • the film materials and PSAs which are coextruded are compositions substantially free (e.g., less than 1 %w) of water and/or solvents.
  • the presence of water or solvents during the coextrusion process can result, and generally does result, in pinholes and bubbles in the coextruded film.
  • the presence of voids in the film due to steam is referred to in the art as "moisture slits.”
  • the hot melt viscosity of the polymeric film materials and of the adhesive should be within a window or range of viscosities which can produce a coextrudate of continuous and uniform layers of the polymeric film material and the adhesive in order to avoid film defects and intermingling of the polymeric film material and the adhesive during the coextrusion process.
  • the polymeric film material have a hot melt viscosity that is within a factor of from about 0.07 to about 1 5 times the hot melt viscosity of the adhesive at the shear rates incurred during the coextrusion process.
  • the shear rates range from about 1 00 to about 1 0,000 sec- 1 . More often the factor is from about 1 to about 1 5.
  • a preferred factor is from 1 to about 10. It is also desirable that the polymer film material and the adhesive have relatively similar melt viscosities at the extrusion temperatures.
  • the extrusion temperatures of the PSA are in the range of from about 1 50° C to about 200°C, and preferably in the range of from about 1 75 ° C to about 200°C. It is, therefore, desired that the polymeric film material selected for use with the PSA have an extrusion temperature below about 200 °C and preferably in the range of from about 1 50° C to about 1 80°C. It is desired in some embodiments that the continuous polymeric films in the constructions of the invention have a high speed tensile strength of at least 1 pound/inch-width, and more often, a high speed tensile strength in the range of from about 2 to about 1 0 pounds/inch-width.
  • High speed tensile strength is determined in accordance with TAPPI Test T494 modified by running the sample at 1 00 ft./l min.
  • the high speed tensile strength of the polymer film should be sufficient, at the given thickness, to permit matrix stripping after die- cutting without undue tearing of the film.
  • the polymeric film material in the constructions of the present invention have an elongation at break of less than about 200%, and more preferably, in the range of from about 1 25% to about 1 75%.
  • a polymeric film material having an ultimate elongation at break greater than about 200% can produce an adhesive construction that is difficult to convert by die-cutting and matrix-stripping, depending on the type of adhesive and polymeric film material, and on their respective coating weights.
  • the key features of the adhesive constructions include ( 1 ) the use of thin polymeric films and (2) adhesive layers having relatively low coat weights.
  • the adhesive constructions are characterized as comprising at least two polymeric films, each with a thickness of from about 0.1 mil up to about 1 .5 or 2 mils, and an adhesive coating weights of less than
  • the adhesive layers have a coat weight in the range of from about 0.5 to about 20 g/m 2 .
  • the thickness of the adhesive layer may range from about 0.02 mils to about 2 mils, and more preferably, between about 0.02 mil and about 1 mil. It should be understood that the thickness and coat weight of both the polymer films and the adhesive layers may vary depending upon the different types of polymer film material and adhesives that are selected, and the properties desired in the adhesive construction. For example, different polymers and different film thicknesses will result in constructions having different stiffnesses.
  • the constructions of the invention should have sufficient Gurley stiffness to permit high speed dispensing, yet be sufficiently flexible to be conformable to most surfaces. Gurley stiffness is determined according to TAPPI Test 543 pm.
  • coextruded adhesive constructions of the first embodiment can provide the structural properties (e.g., strength and stiffness) necessary to facilitate conversion.
  • the coextruded adhesive constructions of the present invention having a polymeric film of the given thicknesses provides an adhesive construction that is, in combination with the adhesive layer, sufficiently self supporting to facilitate conversion (i.e., printing, die-cutting and matrix stripping) .
  • the stiffness of the coextruded adhesive constructions is too low (e.g., less than 1 0 Gurley) to be used satisfactorily in high speed peel-plate dispensing techniques
  • the construction can be dispensed using other techniques or the stiffness can be increased by overlaminating a polymer film to the thin polymer films of the coextruded adhesive construction as described herein.
  • Useful dispensing techniques and dispensing equipment for adhesive constructions of low stiffness are described in U.S. Patents 4,21 7, 1 64, 4,303,461 and 4,896,793 and these patents are incorporated herein for such descriptions.
  • the present invention also provides a process for improving the peel-plate dispensability of a die-cut and matrix-stripped adhesive composite construction prepared from the die cuttable and matrix strippable constructions described above which generally do not have the requisite stiffness to be satisfactorily peel-plate dispensed.
  • it is sometimes difficult to satisfactorily peel-plate dispense labels when the label has a Gurley stiffness in the machine direction of less than 1 5, and more particularly, a Gurley stiffness in the machine direction of less than 10. Labels with insufficient stiffness have a tendency to follow the release liner as the label construction passes over the peel-back edge, and the label is not separated from the release liner as desired.
  • the stiffness of the label construction can be increased, and, accordingly, the ability to dispense such label utilizing a peel-plate can be improved by maintaining the temperature of the label at least about 5 °C below room temperature.
  • the stiffness increases at the selected lower temperature by at least about 1 0 or 1 5 Gurley units. More preferably, the temperature is at or below about 1 5 °C as the leading edge of the label passes over the peel-back edge and the label is separated from the release liner.
  • Label temperatures from about -1 5 ° C to 5 °C or 1 5 °C have been found to be suitable depending on the nature of the polymer and the thickness of the facestock.
  • a reduced temperature temporarily provides the label with a sufficient increase in stiffness to improve its ability to separate from the release liner as the label passes over the peel-back edge.
  • One advantage of this procedure is that the label, after separating from the release liner, and the temperature rises to room temperature, is not as stiff and is conformable as desired for many applications. As mentioned previously, it is a rule of thumb that as the construction stiffness is increased, so is convertibility and dispensability of the construction. However, the conformability of an adhesive construction is known to decrease as the construction stiffness is increase. Thus, the present method for temporarily increasing the stiffness of a label construction to improve its peel-plate dispensability is desirable because the method does not affect the conformability of the label after it is separated from the release liner and applied to an application substrate.
  • the temperature of the label construction or the leading edge of a label can be reduced to below room temperature by a variety of methods.
  • a roll of die-cut and matrix-stripped label construction can be cooled in a cooling room or refrigerator and maintained at this temperature until the labels are dispensed over a peel-plate.
  • Another method for cooling the label construction is to pass it over one or more chill rolls just prior to the peel plate.
  • the peel-plate can be cooled by suitable means, and the temperature of the label is reduced as the label passes over the peel-plate.
  • Chill rolls and peel plates can be cooled by methods known to those skilled in the art.
  • One method uses thermoelectric (TE) coolers such as the line of TE coolers available from Tellurex of Traverse City, New Jersey, under the trade designation ZMAX.
  • the adhesive compositions useful in the constructions of the invention may comprise thermoplastic elastomers comprising at least one thermoplastic elastomeric block copolymer which include linear, branched, grafted or radial block copolymers.
  • the adhesive compositions also contain at least one solid tackifier resin component.
  • a solid tackifier is defined herein as one having a softening point above 80°C.
  • the coextrudable pressure- sensitive adhesive compositions generally comprise from about 40% to about 80% by weight of a thermoplastic elastomer component and from about 20% to about 60% by weight (preferably from about 55% to 65% by weight) of a solid tackifier resin component.
  • Mw molecular weight solid tackifiers
  • attempts to print the polymeric film layer after migration of tackifier or other components from the adhesive layer may result in poor anchorage of the ink and/or blurring of the printing.
  • Migration of the tackifier and other components present in the adhesive layer is a particular problem when the polymer film comprises a polyolefin such as polyethylene.
  • Conventional solid tackifier resins include hydrocarbon resins, rosin, hydrogenated rosin, rosin esters, polyterpene resins, and other resins which exhibit the proper balance of properties.
  • a variety of useful solid tackifier resins are available commercially such as terpene resins which are sold under the trademark Zonatac by Arizona Chemical Company, and petroleum hydrocarbons resins such as the resins sold under the trademark Escorez by Exxon Chemical Company.
  • a useful solid tackifier is Escorez 2596 which is a C 5 -C 9 (aromatic modified aliphatic) synthetic tackifier having an Mw of 21 00 and a dispersity (Mw/Mn) of 2.69.
  • Another useful solid tackifier is Escorez 1 31 0LC, identified as an aliphatic hydrocarbon resin having an Mw of 1 350 and a dispersity of 1 .8.
  • Wingtack 95 is a synthetic tackifier resin available from Goodyear, Akron, Ohio, consisting predominantly of polymerized structure derived from pyperylene and isoprene.
  • the modulus of the adhesive mixtures also may be lowered by the incorporation of liquid rubbers, i.e., liquid at room temperature.
  • the liquid rubbers generally will have an Mw of at least 5,000 and more often at least 20,000.
  • Incorporation of liquid rubbers in amounts of less than 10%, and even less than 5% by weight based on the overall weight of the adhesive formulation results in adhesives which are coextrudable with the polymeric film materials.
  • the incorporation of a liquid rubber also produces an adhesive having increased tack and adhesion.
  • Liquid block copolymers such as liquid styrene-isoprene block copolymers are particularly useful.
  • Kraton LVSI-1 01 available from the Shell Chemical Company, is effective in lowering the modulus of the adhesive, and it has been found, surprisingly, that this liquid styrene- isoprene block copolymer functions as a processing aid, improving the smoothness of the flow of the adhesive from the die.
  • Kraton LVSI-1 01 has a weight average molecular weight of about 40,000.
  • Another example of a useful liquid rubber is a liquid polyisoprene obtained by partially or selectively degrading of high molecular weight polyisoprene.
  • liquid rubber An example of a commercially available partially degraded high molecular weight polyisoprene is Isolene D-400 from Elementis Performance Polymers, Belleville, N.J., and this liquid rubber has an Mw of about 20,000.
  • Other liquid rubbers which may be incorporated into the adhesive mixture include liquid styrene-butadiene rubbers, liquid butadiene rubbers, ethylene-propylene rubbers, etc.
  • the adhesive compositions also may include other materials such as antioxidants, heat and light stabilizers, ultraviolet light absorbers, viscosity modifiers, fillers, colorants, antiblocking agents, reinforcing agents, processing acids, etc.
  • Hindered phenolic and amine antioxidant compounds may be included in the adhesive compositions, and a wide variety of such antioxidant compounds are known in the art. A variety of antioxidants are available from
  • Ciba-Geigy under the general trade designations "Irganox” and “Irgafos”.
  • the hindered phenolic antioxidant n-octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenol)- proprionate is available under the general trade designation
  • Irganox 1076 is identified as Tetrakis (methylene 3-(3',5'-di- tert-butyl-4'-hydroxyphenol) proprionate) methane.
  • Irgafos 1 68 is another useful antioxidant from Ciba-Geigy. Hydroquinone-based antioxidants also may be utilized, and one example of such an antioxidant is 2,5-di-tertiary-amyl-hydroquinone.
  • Ultraviolet absorbers include benzo- triazol derivatives, hydroxy benzyl phenones, esters of benzoic acids, oxalic acid, diamides, etc.
  • Light stabilizers include hindered amine light stabilizers, and the heat stabilizers include dithiocarbamate compositions such as zinc dibutyl dithiocarbamate.
  • the adhesive compositions may contain inorganic fillers and other organic and inorganic additives to provide desired properties.
  • useful fillers include calcium carbonate, titanium dioxide, metal particles, fibers, etc.
  • An example of a reinforcing agent is Cumar
  • the adhesive constructions of the first embodiment of the present invention comprise two layers of a polymeric film and two layers of adhesive layer.
  • the polymeric films may comprise one or more layers.
  • a coextrusion technique useful in preparing an adhesive construction of the first embodiment of the present invention is schematically shown in Fig. 1.
  • the apparatus shown in Fig. 1 utilizes four extruders 10, 11, 12 and 13 which can provide four molten streams (sometimes hereinafter referred to as streams A, B, C and D respectively) of material to the coextrusion die 18.
  • Extruder 10 provides a molten stream 14 of an adhesive composition to the die 18.
  • Extruder 11 provides a molten stream 15 of polymeric film material to the die 18.
  • Extruders 12 and 13 are optional.
  • extruder 12 When present, extruder 12 provides an adhesive stream 16, and extruder 13 provides a molten stream 17 of a polymeric film material, the adhesive and polymer in molten streams 1 6 and 1 7, respectively, may be the same as or different from the adhesive and polymer of molten streams 14 and 1 5.
  • polymer film material is not charged to extruder 1 2, or the polymer charged to extruder 1 2 is the same as that charged to extruder 1 1 , and adhesive is not charged to extruder 1 3.
  • the resulting coextrudate comprises a single layer of polymer film, and a layer of adhesive.
  • the adhesive composites of the first embodiment can be prepared by laminating together two coextrudates prepared in this manner.
  • the extruders 1 0, 1 1 , 1 2 and 1 3 are utilized to blend and melt the compositions and as pumps to deliver the molten streams to the feedblock and the extrusion die. Alternatively, the compositions may be preblended prior to being introduced into the extruders.
  • the precise extruder utilized is not critical to the process. A number of useful extruders are known, and these include single and twin-screw extruders, batch-off extruders, etc. Such extruders are available from a variety of commercial sources including Killion Extruders, Inc.,
  • extrusion dies useful in the invention are the Cloeren "vane” dies, and multimanifold dies available commercially from the Cloeren Company of Orange,
  • the selection of the extrusion die to be utilized in the process of the invention is not critical, certain factors do have an influence on the performance of the extrusion process.
  • the relative viscosities of the materials, and their ability to be processed at a single manifold temperature must be considered.
  • multimanifold dies are typically employed. In multimanifold dies, each material flows in its own manifold to the point of confluence.
  • Each individual manifold also can be designed specifically for the rheology of each polymer resin and/or adhesive, and each manifold also can be controlled at different process temperatures.
  • Multimanifold dies can be designed with zero common land length so that the materials do not meet until the die lip or exit orifice. Alternatively, they can be designed with a short common flow channel. A zero common land would be preferred where the molten streams have extreme viscosity differences and/or temperature requirements. A short common land is generally beneficial because the period of high temperatures and high pressure while the melts are in the common land can improve the bond strength between the layers of the construction.
  • the manifold dies are selected so that the molten streams are joined before the die lip (for example, from about 1 millimeter to about 1 inch before the die lip) .
  • the unified molten structure 20 of two or more layers exits the extrusion die 1 8 through orifice 1 9, and the molten structure is deposited onto a solid substrate 22 (e.g., a release liner) supplied from a roll 21 so that the lower surface of the substrate adhesive layer is in contact with the liner, while the upper surface of the polymeric film is in contact with air.
  • the liner 22 is partially wrapped around the first of a three chill roll stack 23, 23A and 23B. Chill roll 23 also acts as a casting roll.
  • the liner 22 contacts the surface of casting roll 23 and is interposed between the surface of the casting roll and the adhesive layer of the molten stream 20. in the embodiment illustrated in Fig.
  • the molten structure 20 is deposited on the liner 22 and the construction 24 which is formed in the process then passes over chill rolls 23A and 23B and is wound over roll 25 or wound upon itself.
  • the casting/cooling roll 23 and the chill rolls 23A and 23B typically are maintained at a temperature below the temperature of the unified molten structure 20 in order to cool the molten structure after it is deposited on the liner. Typically this temperature is in the range of from about 5 ° to about 100°C, preferably from about 20° to about 30°C.
  • Fig. 1 A is a cross-section of the adhesive construction 24 of one embodiment of the present invention wherein the separation layer is an adhesive.
  • Fig. 1 A comprises a substrate adhesive layer 30, a second polymer film layer 31 , an internal adhesive layer 32, and first polymer film layer 33.
  • Fig. 1 B is a cross-section of an adhesive construction 34 of the present invention wherein the adhesive construction described in Fig. 1 A has a release liner 22 adhesively joined to the lower surface of the substrate adhesive layer 30 of the composite described in Fig. 1 A.
  • Fig. 2 illustrates another coextrusion procedure useful in preparing the constructions of a second embodiment of the present invention.
  • the apparatus shown in Fig. 2 utilizes five extruders 41 , 42, 43, 44 and 45, which provide five molten streams of polymer (sometimes hereinafter referred to as streams A, B, C, D and E respectively) of material.
  • Extruders 41 , 42, 43, 44 and 45 provide molten streams 46, 47, 48, 49 and 50, respectively, to a feedblock 51 .
  • the molten streams of polymer film material exiting the extruders comprise different polymers, or at least adjacent films comprise different polymers.
  • Feedblock 51 in Fig. 2 combines the molten streams of polymeric film material into a single flow channel.
  • the feedblock 51 delivers the molten structure to the extrusion die 52 where the molten structure is reduced in height and increased in width as desired so as to provide a relatively thin and wide construction.
  • An example of a useful feedblock is the Cloeren coextrusion feedblock available commercially from the Cloeren Company of Orange, Texas.
  • the unified molten structure 54 exits the extrusion die 52 through orifice 53, and the molten structure is cooled by passing over cooling roll 55 (several may be used).
  • the coextruded film then is wound over roll 55 of rolled upon itself.
  • a sixth extruder is added to the apparatus described in Fig. 2, and this extruder is utilized to extrude an adhesive layer which is brought into contact with one of the external polymer film layers (e.g., stream 48) within the feed block 51 .
  • the molten stream existing the die comprises the five layers of polymer film as described in Fig. 2, and a layer of adhesive on one outside surface.
  • Fig. 2A is a cross-section of an adhesive construction 54 formed in the process of Fig. 2 and comprises separation layer 63, first stiffening layer 64, second stiffening layer 62, first skin layer 65 and second skin layer 61 .
  • Fig. 2B is a cross-section of a label stock utilizing the composite of Fig. 2A and an adhesive layer 66 and release liner 67.
  • the coextrudate may be uniaxially or biaxially oriented (e.g., by heat stretching and heat setting) . If it is desired to uniaxially or biaxially orient the coextruded adhesive constructions of the present invention, such orientation preferably occurs before the coextrudate is joined with a support material such as a release liner.
  • a support material such as a release liner.
  • the process described with regard to Figs. 1 is modified as follows. The flow of molten material into the die and/or feedblock is rearranged so that the unified molten structures 20 of Fig.
  • the construction may be subjected to orientation followed by lamination to the release surface of a release liner. In one preferred embodiment of the invention, the adhesive constructions are not oriented.
  • Machine direction or biaxial orientation of the cooled cast films of the invention prepared as described above free of a release liner can be accomplished by techniques known in the art.
  • the films can be oriented in the machine direction by using tentering frames where the clips at the edge of the tentering frame travel faster in the machine direction thereby stretching the film in the machine direction.
  • the clips can be programmed to travel faster in the machine direction or to widen in the cross direction, or to stretch in both directions thereby orienting the film in both directions.
  • the edges of the film are preferably free of adhesive so that the clips will not stick to the film.
  • the coextruded adhesive construction then can be laminated to a release liner.
  • the adhesive constructions of the invention can be prepared by (a) separately coextruding two adhesive constructions, each comprising a continuous polymeric film and an adhesive layer as described above and (b) joining the two coextrudates to form a four layer structure of adhesive/film/adhesive/film.
  • the adhesive layer between the two polymeric films shown in Figs. 1 A and 1 B contributes to the adhesive properties of the overall construction, particularly when the interior polymeric film elongates under peel conditions, and the adhesive layer also increases the Gurley stiffness by separating the two film layers.
  • the two continuous polymeric films will have a thickness of from about 0.2 to about 2 mils, and more often from about 0.4 to about 1 .0 mils, and the separation layer will have a thickness of from about 0.02 mil to about 1 .2 mil, and more often from about 0.02 to about 0.8 mils.
  • the adhesive constructions of the present invention such as illustrated in Fig. 1 B and 2B can either be collected for future printing, overlaminating, and converting at a different time and/or geographic location, or these constructions can be routed to one or more other stations for printing, overlaminating, and/or converting during the same operation.
  • the adhesive construction 24 of Fig. 1 is taken up on roll 25 and saved for future printing, overlaminating and/or conversion.
  • the exposed film surface of the adhesive construction of the invention be treated to make the exposed surface of the polymer film more receptive to subsequent printing or marking.
  • the construction is treated by conventional surface treatment methods, such as corona treatment and the like, to increase the surface energy of the polymer film layer to facilitate wetting during the printing process.
  • an important feature of one embodiment of the constructions of the present invention is the ability to deposit printing indicia or other forms of marking on the upper surface of the upper film layer.
  • the polymer film material selected for the exposed or upper surface of the constructions should be one which is receptive to printing with inks using printing techniques such as flexographic printing, screen printing, offset lithography, letter press, thermal transfer, etc., and the applied ink has acceptable adhesion to the surface of the adhesive construction.
  • Example 1 The apparatus utilized in this example is generally similar to the apparatus of Fig. 1 except that it consists of only three extruders (a Killion 1 " single screw extruder (stream A), a 3/4" Brabender single screw extruder (stream B), and a 27 mm Leistritz twin screw extruder in the co-rotating mode (stream Q) and a 6" Cloeren, three layer, three manifold vane die.
  • the adhesive for the adhesive layer of the construction of the invention is fed to the Leistritz twin screw extruder having 9 heated zones which are maintained at 1 45 °C,
  • Escorez 1 31 0 is heated to 1 35 °C and fed at a rate of 543g/hr. into the sixth zone.
  • the twin screw extruder is operated at 450 rpm and requires 2.8 amps.
  • the Brabender extruder operated at 5 rpm is charged with polypropylene 5E66 from Union Carbide.
  • the temperature profile is 1 80°C, 1 90°C and 21 0°C in three zones. Additional polypropylene is charged to the Killion extruder operated at 5 rpm.
  • the third zone of the Killion extruder is heated to 21 0° C.
  • Molten streams from the three extruders are combined inside the Cloeren die set to a temperature of 21 0° C whereby the two molten streams (streams A & B) of polypropylene are disposed on the molten stream of adhesive (stream C), and streams combine inside the die in such a manner that the adhesive containing side will contact a release liner upon exiting the die.
  • the release liner consists of glassine paper coated with GE 7000-series silicone release on one side.
  • the liner is partially wrapped around the bottom-most chill roll (also casting roll) of a three chill roll stack that is maintained in a closed nip position.
  • the chill rolls are maintained at about 22 °C, and the molten stream exiting the die is cast onto the liner wrapped on the bottom-most chill roll.
  • the line speed is about 1 2 m/min.
  • the resulting extrudate is about 1 1 .5 cm. wide and about 0.5 mils (1 2 microns) in thickness.
  • Examples 2-7 Four layer composites are prepared by laminating a first coextrudate which comprises the first skin layer and the adhesive separation layer to a second coextrudate which comprises the second skin layer and the adhesive substrate the thin layer coextrudate.
  • the coextrudates are prepared by the procedure of Example 1 .
  • the two coextrudates are laminated together to form a first skin layer/adhesive separation layer/second skin layer/adhesive substrate layer configuration.
  • composite constructions similar to those prepared in examples 2-7 also can be prepared by simultaneously coextruding the four layers utilizing an apparatus similar to that described in Fig. 1 and by modification of the process of Example 1 .
  • composite construction of examples 2-7 are prepared by coextruding the melted charges through a coextrusion die and casting on cooling rolls.
  • the polymer used in the first skin layer and the second skin layer is polypropylene homopolymer (5E66 available from Union Carbide), and the adhesive used in the adhesive separation layer and the adhesive substrate layer is Adhesive 4 as described above.
  • the control examples comprise only one polymer film layer and one adhesive layer.
  • lamination of the two separately prepared two layer coextrudates results in a four layer construction having significantly increased and unexpectantly high Gurley stiffness. This increase in the stiffness is believed to be due at least in part to the fact that the Young's Modulus of the propylene homopolymer is higher than the Young's Modulus of the adhesive used in the separation layer.
  • Example 3 1 .64 1 .27 1 .0 0.8 54.90 21 .2
  • Example 6 1 .78 0.49 1 .0 0.8 20.90 1 2.6
  • Example 7 1 .71 1 .35 1 .0 0.8 38.6 38.6
  • the Young's Modulus of the separation layer is about 3 orders of magnitude lower than the Young's Modulus of the stiffening layer.
  • the separation layer is the central layer and comprises a blend of 70% of a random propylene copolymer comprising about 96.8% by weight of propylene and about 3.2% by weight of ethylene (Shell Chemical Company).
  • the core or separation layer On both sides of the core or separation layer are stiffening layers which comprise a propylene homopolymer available from Union Carbide under the designation 5E66.
  • the first and second skin layers which are on the outside of the stiffening layers comprise a blend of 50% by weight of the propylene homopolymer and 50% by weight of poly(ethylene vinyl acetate).
  • the first and second stiffening layers and the first and second skin layers are comprised of the same blend of 50% polypropylene and 50% poly(ethylene vinyl acetate).
  • the overall thickness (2.5 mils) is the same as the thickness of Example 9, and the stiffening layer and skin layer on either side of the core separation layer form a single layer of the blend.
  • the thickness ratios of the layers, the overall thickness of the composite, and the Gurley stiffness values for the five layer composites are summarized in the following Table IV
  • the Young's Modulus of the separation layer is about one half the Young's Modulus of the stiffening layer.
  • the composite constructions of the present invention may be combined with a release liner by contacting a release liner with the substrate adhesive layer to form label construction or label stock.
  • the label stock may then be converted to labels by procedures well known to those skilled in the art.
  • the label stock may be printed and die-cut into individual labels.
  • the release liner which may be utilized in the label constructions in the present invention may consist of any of a variety of materials known to those skilled in the art to be suitable as release liners.
  • the release liner comprises a silicone coated paper substrate. Coated polymer film substrates also can be used as release liners.
  • the printing step may occur before or after the combining of the adhesive constructions of the invention and the release liner, but will precede the die-cutting of the facestock into individuals labels.
  • the film must remain in accurate register between printing steps (for example, between successive impressions and different colors) in order that image or text may be of high quality, and between printing and subsequent die-cutting in order that the image or text be located properly on the labels.
  • the film is under tension during printing, and may be subjected to some increase in temperature, such as, for example, when UV inks are curred, and the film must maintain dimensional stability in the machine-direction.
  • the label stock is die-cut into a series of spaced pressure-sensitive labels carried by the release liner.
  • This step may be performed by rotary cutting dies in a well known manner and involves a subsequent stripping of the ladder- shaped matrix of waste or trim materials surrounding the formed labels when they are die-cut (the "rungs" of the ladder representing the spacing between successive labels).
  • the labels then remain on the liner in spaced relation with each other.
  • One failure mode in this operation involves poorly die-cut labels remaining with the matrix as it is stripped. In this mode, as the release levels decrease, poor die-cutting is more likely to cause labels to stay attached to the matrix material and be removed from the liner during matrix stripping along with the matrix. Another failure mode results when the films being die-cut are of insufficient strength. As the strength of the matrix material decreases, the matrix tends to tear as the matrix around the die-cut labels is pulled from the liner.
  • the films of the present invention do have sufficient strength to avoid or reduce breakage of the matrix upstripping.
  • the composite constructions of the present invention have sufficient stiffness to be dispensable utilizing commercially available dispensing apparatus either at room temperature or at lower temperature.
  • the composite constructions are peel-plate dispensable.
  • peel-plate as used herein with regard to dispensing and dispensability is not intended to be limited to plates, but it is intended that the term be understood to include equivalent label separation mechanism such as peel edges, devices with a small radius of curvature, etc.
  • Dispensability includes the steps of the separation of the labels from the liner, and the successful application of the label to a substrate surface.
  • the stiffness of the label when the machine direction stiffness is low and the label cannot be dispensed with a peel-plate at room temperature, the stiffness of the label may be increased sufficiently to enable peel-plate dispensing by reducing the temperature of the label, or at least the leading edge of the label as the label passes over the peel-plate.
  • the effect of temperature on the stiffness of label constructions of the invention is demonstrated by measuring the stiffness (Gurley), at several temperatures, of several samples of composite facestocks with different layer thicknesses.
  • the composite coextruded facestocks used in the following Examples 1 0-1 3 comprise a first polymer film of Vitel 4400B (a copolyester from Bostik having a Tg of 28°C as measured by DSC) and a second polymer film of Vitel 4400B separated by a layer adhesive comprising about 50% adhesive (Quintac 3530 from Nippon Zeon), 45.8% of a tackifier (Escorez 2596) and 4.2% of a liquid rubber (LVSI 1 01 ). Control A does not contain any internal adhesive (no separation layer).
  • the dynamic tensile storage modulus (E') of Vitel 4400 and the adhesive used in Examples 10-13 is measured on a Rheometrics Thermal Instrument using a sample 5 mm wide and 14 mm long.
  • E' is measured in a thin film fixture with the sample oscillated in the machine direction.
  • the adhesive is measured in a shear mode between two plates because of its lower viscosity.
  • Table VI The results of the measurement at several temperatures are reported in Table VI. The results show that the dynamic tensile modulus of the adhesive is less than the dynamic tensile modulus of the Vitel 4400, and the modulus of the Vitel 4400 is 2 to 3 orders of magnitude greater than the modulus of the adhesive.
  • Peel adhesion is the force required to remove a pressure- sensitive label from a panel (stainless steel) at a specified angle and speed.
  • a one inch wide sample of the label construction comprising a facestock and a substrate adhesive as described above is applied to a standard stainless steel panel by mechanically rolling the sample to cause the sample to adhere to the steel panel.
  • the free portion of the label is doubled back at an angle of 1 80°C, and one inch of the label is peeled from the panel at the folded end.
  • the end of the panel from which the label as been removed is clamped into the lower jaw of the adhesion testing machine as specified in PSTC-1 , and the free end of the sample is clamped into the upper jaw.
  • the lower jaw is operated at 1 2 in. per min. As the lower jaw is started in motion, the values obtained while the first inch of sample is mechanically peeled are disregarded. The average peel value obtaining during peeling of the next two inches is recorded as the adhesion value. The peel adhesion values are reported in lbs. or ounces per inch width. The results of the Peel Adhesion Test on the constructions of Example 1 0-1 3 and Control A are shown in the following Table VII.
  • Control A has the same amount of face material (2 mils) and substrate adhesive as Examples 1 1 and 1 3, Control A has a significantly lower 1 80 ° peel.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)

Abstract

Dans l'invention, on utilise une répartition unique d'un matériau polymère formant une pellicule frontale et éventuellement d'un matériau adhésif, en faisant varier l'épaisseur d'une structure composite, ce qui provoque une augmentation de la pellicule frontale et permet d'utiliser moins de matériau d'étiquette, tout en produisant une étiquette présentant une rigidité suffisante pour pouvoir être distribuée par décollement par plaque. Dans un mode de réalisation, l'invention concerne un composite multicouche comprenant une couche de séparation (63) en film polymère présentant une surface supérieure et une surface inférieure, une couche mince supérieure (65) et inférieure (61) en matériau polymère étant déposée respectivement sur les surfaces supérieure et inférieure de la couche de séparation (63), une couche de raidissement (62, 64) étant en outre déposée entre la couche de séparation (63) et chaque couche mince (61, 65). La couche de raidissement (62, 64) comprend un film polymère dont le module de Young est supérieur à celui de la couche de séparation (63), et à celui des couches minces (61, 65), et la couche mince inférieure (61) est pourvue d'une couche adhésive support (66) assemblée à cette couche mince et, à son tour, recouverte d'une couche de libération (67). En outre, l'invention concerne également un procédé d'amélioration de la distribution, par décollement par plaque, d'une structure composite d'étiquettes, consistant à conserver la température d'au moins l'étiquette d'attaque de la structure d'étiquettes, en dessous de 20° C environ, lorsque cette étiquette passe au-dessus de la plaque de décollement et qu'elle se détache de la couche de libération (67).
PCT/US1999/020458 1998-09-04 1999-09-03 Structures composites multicouches Ceased WO2000013887A1 (fr)

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AU58134/99A AU5813499A (en) 1998-09-04 1999-09-03 Composite multilayer constructions

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US14844598A 1998-09-04 1998-09-04
US09/148,445 1998-09-04

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WO2001083212A1 (fr) * 2000-05-02 2001-11-08 Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg Procede de fabrication d"un produit coextrude a plusieurs couches et structure en feuille obtenue selon ledit procede
US7306844B2 (en) 2004-03-10 2007-12-11 Avery Dennison Corporation Labels and labeling process
WO2009092640A1 (fr) * 2008-01-22 2009-07-30 Tesa Se Film support, notamment pour bande adhésive et utilisation correspondante
WO2011160627A1 (fr) * 2010-06-22 2011-12-29 Danapak Flexibles A/S Feuille, procédé de fabrication et d'utilisation d'une feuille comme couvercle pour emballages
US20120034402A1 (en) * 2009-03-30 2012-02-09 Avery Dennison Corporation Removable Adhesive Label Containing Polymeric Film Layer Having Water Affinity
EP2578395A1 (fr) * 2011-10-04 2013-04-10 Rkw Se Construction de film d'étiquette multicouche pour étiquettes sensibles à la pression
US20130199700A1 (en) * 2012-02-02 2013-08-08 Avery Dennison Corporation Low Modulus Shrink Compliant Films
EP2716453A1 (fr) * 2009-02-25 2014-04-09 Avery Dennison Corporation Support d'impression multicouche fabriqué par revêtement par extrusion
WO2016028862A1 (fr) * 2014-08-19 2016-02-25 Avery Dennison Corporation Système raidisseur d'étiquette pour rayonnage et affichages de produits
US9315064B2 (en) 2012-02-20 2016-04-19 Avery Dennison Corporation Multilayer film for multi-purpose inkjet systems
US9334425B2 (en) 2009-03-30 2016-05-10 Avery Dennison Corporation Removable adhesive label containing high tensile modulus polymeric film layer
US9387652B2 (en) 2005-01-10 2016-07-12 Avery Dennison Corporation Removable curl labels
US9422465B2 (en) 2006-11-02 2016-08-23 Avery Dennison Corporation Emulsion adhesive for washable film
US9752022B2 (en) 2008-07-10 2017-09-05 Avery Dennison Corporation Composition, film and related methods
CN108000156A (zh) * 2017-11-28 2018-05-08 昆山天卓贸易有限公司 一种薄金属板的剪切折弯设备
US10157554B2 (en) 2009-03-30 2018-12-18 Avery Dennison Corporation Removable adhesive label containing inherently shrinkable polymeric film
US10703131B2 (en) 2010-03-04 2020-07-07 Avery Dennison Corporation Non-PVC film and non-PVC film laminate
US10919273B2 (en) * 2006-10-16 2021-02-16 Swimc Llc Multilayer thermoplastic film
CN113165341A (zh) * 2018-12-03 2021-07-23 王子控股株式会社 层叠体及层叠体的制造方法
US11485162B2 (en) 2013-12-30 2022-11-01 Avery Dennison Corporation Polyurethane protective film
CN116323844A (zh) * 2020-10-09 2023-06-23 德莎欧洲股份公司 具有胶带和两层衬垫的层状构造体

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US7648608B2 (en) 2000-05-02 2010-01-19 Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg Method for producing a multilayer coextrudate and a film structure produced by this method
WO2001083212A1 (fr) * 2000-05-02 2001-11-08 Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg Procede de fabrication d"un produit coextrude a plusieurs couches et structure en feuille obtenue selon ledit procede
US7306844B2 (en) 2004-03-10 2007-12-11 Avery Dennison Corporation Labels and labeling process
US9387652B2 (en) 2005-01-10 2016-07-12 Avery Dennison Corporation Removable curl labels
US10919273B2 (en) * 2006-10-16 2021-02-16 Swimc Llc Multilayer thermoplastic film
US10590315B2 (en) 2006-11-02 2020-03-17 Avery Dennison Corporation Emulsion adhesive for washable film
US9422465B2 (en) 2006-11-02 2016-08-23 Avery Dennison Corporation Emulsion adhesive for washable film
WO2009092640A1 (fr) * 2008-01-22 2009-07-30 Tesa Se Film support, notamment pour bande adhésive et utilisation correspondante
CN101978010A (zh) * 2008-01-22 2011-02-16 德莎欧洲公司 载体膜，特别是用于胶带的载体膜，及其用途
US9752022B2 (en) 2008-07-10 2017-09-05 Avery Dennison Corporation Composition, film and related methods
EP2716453A1 (fr) * 2009-02-25 2014-04-09 Avery Dennison Corporation Support d'impression multicouche fabriqué par revêtement par extrusion
US9682540B2 (en) 2009-02-25 2017-06-20 Avery Dennison Corporation Method for making multi-layer print media by extrusion coating
US20120034402A1 (en) * 2009-03-30 2012-02-09 Avery Dennison Corporation Removable Adhesive Label Containing Polymeric Film Layer Having Water Affinity
US10157554B2 (en) 2009-03-30 2018-12-18 Avery Dennison Corporation Removable adhesive label containing inherently shrinkable polymeric film
US9334425B2 (en) 2009-03-30 2016-05-10 Avery Dennison Corporation Removable adhesive label containing high tensile modulus polymeric film layer
US10902750B2 (en) 2009-03-30 2021-01-26 Avery Dennison Corporation Removable adhesive label containing inherently shrinkable polymeric film
US10002549B2 (en) 2009-03-30 2018-06-19 Avery Dennison Corporation Removable adhesive label containing polymeric film layer having water affinity
US10703131B2 (en) 2010-03-04 2020-07-07 Avery Dennison Corporation Non-PVC film and non-PVC film laminate
WO2011160627A1 (fr) * 2010-06-22 2011-12-29 Danapak Flexibles A/S Feuille, procédé de fabrication et d'utilisation d'une feuille comme couvercle pour emballages
WO2013050119A1 (fr) * 2011-10-04 2013-04-11 Rkw Se Films multicouches pour pellicule adhésive d'étiquettes
EP2578395A1 (fr) * 2011-10-04 2013-04-10 Rkw Se Construction de film d'étiquette multicouche pour étiquettes sensibles à la pression
AU2013214953B2 (en) * 2012-02-02 2016-07-21 Avery Dennison Corporation Low modulus shrink compliant labels
WO2013116612A1 (fr) * 2012-02-02 2013-08-08 Avery Dennison Corporation Films conformes thermorétractables à faible coefficient de réduction
US20130199700A1 (en) * 2012-02-02 2013-08-08 Avery Dennison Corporation Low Modulus Shrink Compliant Films
US9315064B2 (en) 2012-02-20 2016-04-19 Avery Dennison Corporation Multilayer film for multi-purpose inkjet systems
US11485162B2 (en) 2013-12-30 2022-11-01 Avery Dennison Corporation Polyurethane protective film
US11872829B2 (en) 2013-12-30 2024-01-16 Avery Dennison Corporation Polyurethane protective film
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CN116323844A (zh) * 2020-10-09 2023-06-23 德莎欧洲股份公司 具有胶带和两层衬垫的层状构造体

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