Pressure sensitive shrink label

Description

TECHNICAL FIELD

This invention relates to pressure sensitive shrink labels. More specifically, the invention relates to pressure sensitive labels that have superior conformability to containers having complex shapes and methods for applying such labels.

BACKGROUND

It is common practice to apply labels to containers or bottles to provide information such as the supplier of the container or the contents of the container. Such containers and bottles are available in a wide variety of shapes and sizes for holding many different types of materials such as detergents, chemicals, personal care products, motor oil, beverages, etc.

Polymeric film materials and film facestocks have been described for use as labels in various fields. Polymeric labels are increasingly desired for many applications, particularly clear polymeric labels since they provide a no-label look to decorated glass and plastic containers. Paper labels block the visibility of the container and/or the contents in the container. Clear polymeric labels enhance the visual aesthetics of the container, and therefore the product, and are growing much faster than paper labels in the package decoration market as consumer product companies are continuously trying to upgrade the appearance of their products. Polymeric film labels also have superior mechanical properties, such as tensile strength and abrasion resistance.

Traditional pressure sensitive adhesive (PSA) labels often have difficulty adhering smoothly to containers having curved surfaces and/or complex shapes without wrinkling, darting or lifting on the curved surfaces. The label size of typical PSA labels is limited to no larger than ¼ inch (6.35 mm) away from the edge (beginning) of curvature of a container or article. Shrink sleeve labels have typically been used on these types of compound containers. Labeling operations are carried out using processes and methods that require the formation of a tube or sleeve of the heat shrink film that is placed over the container and heated in order to shrink the film to conform to the size and shape of the container. Alternatively, the containers are completely wrapped with a shrink label using a process wherein the shrink film is applied to the container directly from a continuous roll of film material and then heat is applied to conform the wrapped label to the container. However, label defects can occur during labeling operations of simple or compound shaped bottles during application or in post application processes. These misapplied labels result in high scrap or extra processing steps that can be costly.

The present invention provides a pressure sensitive adhesive label that can be applied to containers and articles on complex shapes and compound curves with less material required and less cost than for shrink sleeve or shrink wrap labels. In addition, the labels of the present invention enable the user to expand the billboard or graphics region of traditional pressure sensitive labels on containers and articles having complex shapes and/or compound curves.

SUMMARY

A label for application on a curved or nonplanar surface comprising a heat shrink film and a pressure sensitive adhesive is provided. In one embodiment, there is provided a pressure sensitive adhesive label for application on a surface having at least one compound curve, the label comprising: a heat shrinkable film having an inner surface and outer surface, and a machine direction and a transverse direction, the film having an ultimate shrinkage S in at least one direction of at least 10% at 90° C., wherein the shrinkage in the other direction is S±20%; and a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film. The shrink film has moderate and balanced shrink in both the machine direction and the transverse direction. In one embodiment, the film has an ultimate shrinkage S in at least one direction of at least 10% at 90° C., and the shrinkage in the other direction is S±10%. The label may further include a release liner removal adhered to the adhesive layer.

There is also provided an article bearing a label comprising: an article having a surface comprising at least one compound curve; and a pressure sensitive label comprising a heat shrinkable film having an inner surface and outer surface, and a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film, wherein the label is applied to at least one compound curve.

A method of applying a label to an article wherein the article has a surface having at least one compound curve is provided. The method comprises: (a) providing an article having a surface comprising at least one compound curve; (b) providing a label comprising (i) a heat shrinkable film having an inner surface and outer surface and (ii) a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film, wherein the label has a central portion and a peripheral portion; (c) contacting the adhesive layer of the central portion of the label with the article; (d) applying pressure to the label in an outward direction from the central portion to the peripheral portion, wherein at least a portion of the label is applied to at least one compound curve of the article; and (e) applying heat to at least a portion of the label to shrink at least that portion of the label and adhere the label to the article. After or during the application of heat, the label may be further compressed or wiped down to fully adhere the label to the article and eliminate any remaining defects in the label.

In one aspect of the invention, there is provided a method of applying a label to an article, the method including the steps of: providing an article having a surface including at least one compound curve; providing a label including (i) a heat shrinkable film having an inner surface and an outer surface; and (ii) a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film, wherein the label has a first edge and a contact region; contacting the adhesive layer in the contact region with the article; applying heat and pressure simultaneously to the label in a direction from the contact region to the first edge such that the first edge of the label adheres to article and the label shrinks to conform to the compound curve of the article, wherein the heat and pressure are applied by a heated conformable membrane.

The heated and pressure is applied to the label, in one embodiment, by a walking beam that includes a conformable heated bladder. The heated bladder may be expandable.

In another embodiment, heat and pressure are applied by a walking beam that includes a heated cavity wherein the shape of the cavity corresponds to the shape of the article to which the label is applied.

In one embodiment, heat and pressure are applied by a walking beam that includes a flexible heated membrane suspended between at least two frame members. The heated membrane may be porous or non-porous. The porous membrane may include a mesh screen.

In yet another embodiment, heat and pressure are applied by a walking beam that includes a flexible heated membrane mounted to a rectangular frame. The walking beam may alternatively include a flexible heated membrane mounted to a frame having a shape corresponding to the shape of the article to which the label is applied.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates a front view of a container to which the label of the present invention has been applied as compared to prior art pressure sensitive labels.

FIG. 2A to 2D illustrates the labeled container before and after the application of heat to the label.

FIG. 3A to 3D illustrate embodiments of containers having complex shapes and compound curves to which the label of the present invention is applied.

FIGS. 4A and 4B illustrate front views of embodiments of containers having irregular surfaces.

FIG. 5 is a three dimensional view of a portion of a labeled article having a compound curve.

FIGS. 6A-6D schematically illustrate the process of applying the label to an article having a compound curve.

FIGS. 7A and 7B schematically illustrate an embodiment of the process of applying a label to an article wherein a walking beam is used.

FIG. 8 is a top view of a walking beam conveyor having a heated bladder.

FIGS. 9A and 9B are a schematic view of a heated cavity containment box of a walking beam conveyor.

FIG. 10 is a schematic view of a walking beam conveyor arm having a draped flexible membrane.

FIGS. 11A and 11B are schematic views of a rectangular framed containment box of a walking beam conveyor having a heated membrane.

FIGS. 12A and 12B are schematic views of a framed containment box of a walking beam conveyor having a heated membrane, wherein the shape of the frame corresponds to the shape of the article to be labeled.

FIG. 13 is a schematic view of a walking beam conveyor having a porous membrane.

FIGS. 14A and 14B are side views of a walking beam containment box including an expandable bladder.

DETAILED DESCRIPTION

Pressure sensitive adhesive labels are provided that can improve the appearance of labeled containers and articles by conforming to the contours of the container or article and by providing an enlarged billboard appearance. End users and product designers must currently alter their designs to accommodate the limitations of traditional product decorating technologies. The labels of the present invention provide the designers with more freedom in product designs to create more shelf appeal and to carry more information.

Containers and articles with compound curves typically have to be fully wrapped with shrink film in order to label or decorate the article. The labels of the present invention are capable of expanding the label over complex curves without having to fully wrap the article. This partial label coverage impacts the product cost as well as the product appearance. Typical pressure sensitive labels cannot be applied to containers and articles without undesirable darting and wrinkling of the label. “Darting” is defined as the accumulation of excess label material that rises up away from the article to which the label is applied.

The labels of the present invention provide significant processing advantages over traditional shrink labels. For example, the pressure sensitive shrink labels of the present invention allow for more traditional printing and secondary processes such as foils and hot stamping. Where typical shrink labels must be subsurface printed, the labels of the present invention can be surface printed, which enhances the color quality, sharpness and texture of the printed image. The label film may be printed by water flexographic, UV flexographic, UV letterpress, UV screen, solvent gravure and hot foil stamp.

The pressure sensitive labels comprise (a) a heat shrinkable polymeric film having an inner surface and an outer surface and a machine direction and a transverse direction; and (b) a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film. The shrinkage of the heat shrinkable polymeric film is balanced in the machine direction and the transverse direction. In at least one direction, the ultimate shrinkage (S) is at least 10% at 90° C. and in the other direction, the shrinkage is S±20%. As an illustration of balanced shrinkage, if the shrinkage in the machine direction is 40% at 105° C., then the shrinkage in the transverse direction is 40%±20%, or within the range of 20% to 60% at 105° C. In one embodiment, the ultimate shrinkage (S) is at least 10% at 90° C. and in the other direction, the shrinkage is S±10%. As used herein, the term “ultimate shrinkage” means the maximum shrinkage the film is capable of achieving at a particular shrink temperature, as measured by ASTM Method D 1204.

The labels are not provided as a shrink sleeve or tube that encapsulates the entire article or as a shrink wrap label that wraps around the article and forms a seam wherein the ends of the label meet. The present labels may be provided in a variety of shapes to suit the article or container to which they are applied, giving the container designer greater latitude in container configuration and label design than with traditional pressure sensitive labels or with shrink wrap or shrink sleeve labels. The labels may be cut into the desired shape by any known method, including, for example, die cutting and laser cutting. In one embodiment, the label is die cut to a specific configuration that compensates for the shrinkage of the label and the shape of the article to which it is applied.

Because the label is conformable, the billboard or graphics area of the labeled container can be extended further onto the container edges and onto compound curved areas of the container. The label may be 10% to 30% larger than a standard PSA label. As used herein, the term “compound curve” means a surface having no direction for which there is no curvature. For example, the surface of a sphere or the surface of an ellipsoid has curvature in every direction, and therefore has compound curves. A cylinder, on the other hand, has a surface for which there is at least one direction for which there is no curvature. Thus, a simple cylinder does not have compound curves.

FIG. 1 illustrates the expanded billboard area of the pressure sensitive shrink label of the present invention. Bottle 10 has pressure sensitive shrink label 12 adhered thereto. The dashed line 14 indicates the outer boundary of standard pressure sensitive labels. A standard (i.e., non-shrink) pressure sensitive label cannot extend onto the areas of the bottle having the compound curves 16 (the area between the inner dashed line and the outer solid line). When label 12 is initially applied to the bottle 10, darts and pleats may form near the perimeter of the label in the areas of the bottle having compound curves 16.

Once the pressure sensitive label is applied to the container, heat is applied as needed to eliminate any label application defects such as darts, edge lift and wrinkles. In one embodiment, pressure and/or wipe down may be used in addition to the application of heat to eliminate any defects.

Referring to FIGS. 2A-2D, the present label and method for applying the label are illustrated. In FIGS. 2A and 2B, a label 12 that includes a shrink film having a continuous layer of pressure sensitive adhesive applied thereto is applied to a container 10 having compound curves around the circumference of the container, and then wiped down. No heat is applied to the label. The label 12 extends onto the compound curves 16 where darts 18 are formed near the perimeter 20 of the label. FIGS. 2C and 2D show the labeled container of FIGS. 2A-2B after heat is applied to the label. The darts 18 have been eliminated and the label 12 conforms to the compound curves of the container 10 near the label perimeter 20 without any defects.

The article or container to which the label is applied can be provided in a variety of forms or shapes. Non-limiting examples of suitable articles include containers with and without closures, trays, lids, toys, appliances, etc. The article or container may be made of any conventional polymer, glass, or metal such as aluminum. Examples of suitable polymeric materials include high density polyethylene (HDPE), low density polyethylene (LDPE), polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride, polycarbonate, nylon, fluorinated ethylene propylene, polystyrene, etc. The article or container can be made by a number of various processes known in the art, such as blow molding, injection molding, thermoforming, rotational molding and the like.

Useful containers include, for example, a bottle having a closure on the top of the bottle, an upside down bottle having a closure on the bottom of the bottle, a bottle with a pump dispenser or a foaming dispenser, a tube with a closure and a bottle with a closure.

The container or article may have a transparent appearance. In one embodiment, the container or article has a translucent appearance. The translucent appearance can be achieved by, for example, treatments of the transparent container or article, the addition of ingredients such as dyes and pearlescent agents to base polymers, the use of polypropylene and/or polyethylene that are mixed with clarifying agents. The treatments include, for example, spray coating, sandblasting, and mold surface treatment.

The container or article may include aesthetic features, including, for example, textures, embossing, lenticular lens, colors, holograms, frosted or matte color, etc. The surface of the container or article may be treated prior to application of the label. For example, the surface of the container or article may be flame treated or a primer coating may be applied.

FIGS. 3A, 3B and 3C each illustrate a container having a complex shape and compound curves. FIG. 3A is a front view of a container 30a having a symmetrical, spherical shape wherein the container has a tapered concave area 32 at the top and a wider convex area 33 toward the bottom. Typically, a shrink sleeve would be used to provide a functional label for this container. With the present invention, a pressure sensitive shrink label 31 can be smoothly applied to container 30a without the appearance of label defects. FIG. 3B is a front view of a container 30b having an asymmetrical shape wherein one side of the container has both a concave area 34 and a convex area 35 and the opposing side curves in a substantially similar manner along the length of the container. The conventional method of labeling container 30b would be to apply a shrink sleeve label to conform to the complex shape of the container. A pressure sensitive shrink label 31 can be applied to the container 30b to provide sufficient billboard area with much less label material. FIG. 3C is a front view of a container 30c that is an upside down bottle having a closure 36 at the bottom and label 31 applied to the front surface. FIG. 3D is a side view of container 30c. The areas 37 within the dashed lines indicate the outer boundaries of standard pressure sensitive labels that can be applied to the container. The complex shape of this container requires two separate standard pressure sensitive labels to decorate the container, as the application of one continuous standard pressure sensitive label would result in the formation of darts and pleat defects. Pressure sensitive shrink label 31 can cover a much larger area, which provides more design options for the product designer.

FIGS. 4A and 4B each illustrate a container having an irregular surface. FIG. 4A is a front view of a container 40a having raised ridges 42 along one side of the container. The opposing side of the container has a smooth surface. FIG. 4B is a front view of a container 40b having circumferentially recessed rings 43 along the length of the container. It should be noted that cylindrically shaped articles having areas of compound curves such as containers 40a and 40b are not excluded from the articles claimed herein.

FIG. 5 is a schematic three dimensional view of a portion of a container to which the label has been applied. The container 50 has surface comprising a compound curve. Label 52 is applied to the container and covers a portion of the compound curved area. Line 54 indicates the outer boundary to which typical pressure sensitive labels can be applied with out the formation of defects in the label. Area 56 indicates the expanded billboard area that is obtainable with the present labels without the formation of defects such wrinkles, edge lift or darts.

Shrink Film

The polymeric films useful in the label constructions of the present invention possess balanced shrink properties. The balanced shrink properties allow the film to tighten darts and wrinkles initially formed in the label when the label is applied over curved surfaces and allow the darts and wrinkles to be wiped down with minimal graphics distortion of the label. Films having unbalanced shrink, that is, films having a high degree of shrink in one direction and low to moderate shrink in the other direction are not particularly useful because while darts may be removed in one direction, in the other direction the formation of darts is exacerbated. Useful films having balanced shrink allow for a wider variety of label shapes to be applied to a wider variety of container shapes.

In one embodiment, the polymeric film has an ultimate shrinkage (S) as measured by ASTM procedure D1204 in at least one direction of at least 10% at 90° C. and in the other direction, the shrinkage is S±20%. In another embodiment, the film has an ultimate shrinkage (S) in at least one direction of about 10% to about 50% at 70° C. and in the other direction, the shrinkage is S±20%. In one embodiment, the ultimate shrinkage (S) is at least 10% at 90° C. and in the other direction, the shrinkage is S±10%. The shrink initiation temperature of the film, in one embodiment, is in the range of about 60° C. to about 80° C.

The shrink film must be thermally shrinkable and yet have sufficient stiffness to be dispensed using conventional labeling equipment and processes, including printing, die-cutting and label transfer. The stiffness of the film required depends on the size of the label, the speed of application and the labeling equipment being used. In one embodiment, the shrink film has a stiffness in the machine direction (MD) of at least 5 mN, as measured by the L&W Bending Resistance test. In one embodiment, the shrink film has a stiffness of at least 10 mN, or at least 20 mN. The stiffness of the shrink film is important for proper dispensing of labels over a peel plate at higher line speeds.

In one embodiment, the die-cut labels are applied to the article or container in an automated labeling line process at a line speed of at least 100 units per minute, or at least 250 units per minute or at least 500 units per minute.

In one embodiment, the shrink film has a 2% secant modulus as measured by ASTM D882 in the machine direction (MD) of about 20,000 to about 400,000 psi, and in the transverse (or cross) direction (TD) of about 20,000 to about 400,000 psi. In another embodiment, the 2% secant modulus of the film is about 30,000 to about 300,000 in the machine direction and about 30,000 to about 300,000 in the transverse direction. The film may have a lower modulus in the transverse direction than in the machine direction so that the label is easily dispensed (MD) while maintaining sufficiently low modulus in the TD for conformability and/or squeezability.

The polymeric film may be made by conventional processes. For example, the film may be produced using a double bubble process, tenter process or may comprise a blown film.

The shrink film useful in the label may be a single layer construction or a multilayer construction. The layer or layers of the shrink film may be formed from a polymer chosen from polyester, polyolefin, polyvinyl chloride, polystyrene, polylactic acid, copolymers and blends thereof.

Polyolefins comprise homopolymers or copolymers of olefins that are aliphatic hydrocarbons having one or more carbon to carbon double bonds. Olefins include alkenes that comprise 1-alkenes, also known as alpha-olefins, such as 1-butene and internal alkenes having the carbon to carbon double bond on nonterminal carbon atoms of the carbon chain, such as 2-butene, cyclic olefins having one or more carbon to carbon double bonds, such as cyclohexene and norbornadiene, and cyclic polyenes which are noncyclic aliphatic hydrocarbons having two or more carbon to carbon double bonds, such as 1,4-butadiene and isoprene. Polyolefins comprise alkene homopolymers from a single alkene monomer, such as a polypropylene homopolymer, alkene copolymers from at least one alkene monomer and one or more additional olefin monomers where the first listed alkene is the major constituent of the copolymer, such as a propylene-ethylene copolymer and a propylene-ethylene-butadiene copolymer, cyclic olefin homopolymers from a single cyclic olefin monomer, and cyclic olefin copolymers from at least one cyclic olefin monomer and one or more additional olefin monomers wherein the first listed cyclic olefin is the major constituent of the copolymer, and mixtures of any of the foregoing olefin polymers.

In one embodiment, the shrink film is a multilayer film comprising a core layer and at least one skin layer. The skin layer may be a printable skin layer. In one embodiment, the multilayer shrink film comprises a core and two skin layers, wherein in at least one skin layer is printable. The multilayer shrink film may be a coextruded film.

The film can range in thickness from 0.5-20, or 0.5-12, or 0.5-8, or 1-3 mils. The difference in the layers of the film can include a difference in thermoplastic polymer components, in additive components, in orientation, in thickness, or a combination thereof. The thickness of the core layer can be 50-95%, or 60-95% or 70-90% of the thickness of the film. The thickness of a skin layer or of a combination of two skin layers can be 5-50%, or 5-40% or 10-30% of the thickness of the film.

The film can be further treated on one surface or both the upper and lower surfaces to enhance performance in terms of printability or adhesion to an adhesive. The treatment can comprise applying a surface coating such as, for example, a lacquer, applying a high energy discharge to include a corona discharge to a surface, applying a flame treatment to a surface, or a combination of any of the foregoing treatments. In an embodiment of the invention, the film is treated on both surfaces, and in another embodiment the film is treated on one surface with a corona discharge and is flame treated on the other surface.

The layers of the shrink film may contain pigments, fillers, stabilizers, light protective agents or other suitable modifying agents if desired. The film may also contain anti-block, slip additives and anti-static agents. Useful anti-block agents include inorganic particles, such as clays, talc, calcium carbonate and glass. Slip additives useful in the present invention include polysiloxanes, waxes, fatty amides, fatty acids, metal soaps and particulate such as silica, synthetic amorphous silica and polytetrafluoroethylene powder. Anti-static agents useful in the present invention include alkali metal sulfonates, polyether-modified polydiorganosiloxanes, polyalkylphenylsiloxanes and tertiary amines.

In one embodiment, the shrink film is microperforated to allow trapped air to be released from the interface between the label and the article to which it is adhered. In another embodiment, the shrink film is permeable to allow fluid to escape from the adhesive or from the surface of the article to escape. In one embodiment, vent holes or slits are provided in the shrink film.

Adhesives

A description of useful pressure sensitive adhesives may be found in Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-Interscience Publishers (New York, 1988). Additional description of useful PSAs may be found in Polymer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964). Conventional PSAs, including acrylic-based PSAs, rubber-based PSAs and silicone-based PSAs are useful. The PSA may be a solvent based or may be a water based adhesive. Hot melt adhesives may also be used. In one embodiment, the PSA comprises an acrylic emulsion adhesive.

The adhesive and the side of the film to which the adhesive is applied have sufficient compatibility to enable good adhesive anchorage. In one embodiment, the adhesive is chosen so that the labels may be cleanly removed from PET containers up to 24 hours after application. The adhesive is also chosen so that the adhesive components do not migrate into the film.

In one embodiment, the adhesive may be formed from an acrylic based polymer. It is contemplated that any acrylic based polymer capable of forming an adhesive layer with sufficient tack to adhere to a substrate may function in the present invention. In certain embodiments, the acrylic polymers for the pressure-sensitive adhesive layers include those formed from polymerization of at least one alkyl acrylate monomer containing from about 4 to about 12 carbon atoms in the alkyl group, and present in an amount from about 35-95% by weight of the polymer or copolymer, as disclosed in U.S. Pat. No. 5,264,532. Optionally, the acrylic based pressure-sensitive adhesive might be formed from a single polymeric species.

The glass transition temperature of a PSA layer comprising acrylic polymers can be varied by adjusting the amount of polar, or “hard monomers”, in the copolymer, as taught by U.S. Pat. No. 5,264,532, incorporated herein by reference. The greater the percentage by weight of hard monomers is an acrylic copolymer, the higher the glass transition temperature. Hard monomers contemplated useful for the present invention include vinyl esters, carboxylic acids, and methacrylates, in concentrations by weight ranging from about zero to about thirty-five percent by weight of the polymer.

The PSA can be acrylic based such as those taught in U.S. Pat. No. 5,164,444 (acrylic emulsion), U.S. Pat. No. 5,623,011 (tackified acrylic emulsion) and U.S. Pat. No. 6,306,982. The adhesive can also be rubber-based such as those taught in U.S. Pat. No. 5,705,551 (rubber hot melt). It can also be radiation curable mixture of monomers with initiators and other ingredients such as those taught in U.S. Pat. No. 5,232,958 (UV cured acrylic) and U.S. Pat. No. 5,232,958 (EB cured). The disclosures of these patents as they relate to acrylic adhesives are hereby incorporated by reference.

Commercially available PSAs are useful in the invention. Examples of these adhesives include the hot melt PSAs available from H.B. Fuller Company, St. Paul, Minn. as HM-1597, HL-2207-X, HL-2115-X, HL-2193-X. Other useful commercially available PSAs include those available from Century Adhesives Corporation, Columbus, Ohio. Another useful acrylic PSA comprises a blend of emulsion polymer particles with dispersion tackifier particles as generally described in Example 2 of U.S. Pat. No. 6,306,982. The polymer is made by emulsion polymerization of 2-ethylhexyl acrylate, vinyl acetate, dioctyl maleate, and acrylic and methacrylic comonomers as described in U.S. Pat. No. 5,164,444 resulting in the latex particle size of about 0.2 microns in weight average diameters and a gel content of about 60%.

A commercial example of a hot melt adhesive is H2187-01, sold by Ato Findley, Inc., of Wauwatusa, Wis. In addition, rubber based block copolymer PSAs described in U.S. Pat. No. 3,239,478 also can be utilized in the adhesive constructions of the present invention, and this patent is hereby incorporated by a reference for its disclosure of such hot melt adhesives that are described more fully below.

In another embodiment, the pressure-sensitive adhesive comprises rubber based elastomer materials containing useful rubber based elastomer materials include linear, branched, grafted, or radial block copolymers represented by the diblock structure 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. These 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 that may be monocyclic or bicyclic in nature. Rubbery materials such as polyisoprene, polybutadiene, and styrene butadiene rubbers may be used to form the rubbery block or segment. Particularly useful 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 that may be utilized include any of those that exhibit elastomeric properties. The block copolymers may be diblock, triblock, multiblock, starblock, polyblock or graftblock copolymers. Throughout this specification, 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, (1985) John Wiley & Sons, Inc., New York, pp. 325-326, and by J. E. McGrath in Block Copolymers, Science Technology, Dale J. Meier, Ed., Harwood Academic Publishers, 1979, at pages 1-5.

Such block copolymers may contain various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up to about 40% by weight of vinyl aromatic hydrocarbon. Accordingly, 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. Pat. Nos. 3,251,905; 3,390,207; 3,598,887; and 4,219,627. As well known, 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. Pat. Nos. 3,251,905; 3,639,521; and 4,208,356, the disclosures of which are hereby incorporated by reference.

Conjugated dienes that may be utilized to prepare the polymers and copolymers are those containing from 4 to about 10 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, 1,3-pentadiene, 1,3-hexadiene, etc. Mixtures of these conjugated dienes also may be used.

Examples of 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-dimethylstyrene, alpha-methylstyrene, beta-methylstyrene, p-isopropylstyrene, 2,3-dimethylstyrene, o-chlorostyrene, p-chlorostyrene, o-bromostyrene, 2-chloro-4-methylstyrene, etc.

Many of the above-described copolymers of conjugated dienes and vinyl aromatic compounds are commercially available. The number average molecular weight of the block copolymers, prior to hydrogenation, is from about 20,000 to about 500,000, or from about 40,000 to about 300,000.

The average molecular weights of the individual blocks within the copolymers may vary within certain limits. In most instances, the vinyl aromatic block will have a number average molecular weight in the order of about 2000 to about 125,000, or 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, or from about 35,000 to 150,000.

Also, prior to hydrogenation, the vinyl content of the conjugated diene portion generally is from about 10% to about 80%, or 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.

Specific examples of diblock copolymers include styrene-butadiene (SB), styrene-isoprene (SI), and the hydrogenated derivatives thereof. Examples of triblock polymers include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), alpha-methylstyrene-butadiene-alpha-methylstyrene, and alpha-methylstyrene-isoprene alpha-methylstyrene. Examples of commercially available block copolymers useful as the adhesives in the present invention include those available from Kraton Polymers LLC under the KRATON trade name.

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.

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. Pat. Nos. 3,113,986 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 0.5% to about 20% of their original unsaturation content prior to hydrogenation.

In one embodiment, 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/propylene)-styrene block polymer. When 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. When such a block copolymer is hydrogenated, the resulting product resembles a regular copolymer block of ethylene and 1-butene (EB). As noted above, when the conjugated diene employed as isoprene, the resulting hydrogenated product resembles a regular copolymer block of ethylene and propylene (EP).

A number of selectively hydrogenated block copolymers are available commercially from Kraton Polymers under the general trade designation “Kraton G.” One example is Kraton G1652 which is a hydrogenated SBS triblock comprising about 30% by weight of styrene end blocks and a midblock which is a copolymer of ethylene and 1-butene (EB). A lower molecular weight version of G1652 is available under the designation Kraton G1650. Kraton G1651 is another SEBS block copolymer which contains about 33% by weight of styrene. Kraton G1657 is an SEBS diblock copolymer which contains about 13% w styrene. This styrene content is lower than the styrene content in Kraton G1650 and Kraton G1652.

In another embodiment, the selectively hydrogenated block copolymer is of the formula:

B_n(AB)_oA_p

wherein n=0 or 1; o is 1 to 100; p is 0 or 1; each B prior to hydrogenation is predominantly a polymerized conjugated diene hydrocarbon block having a number average molecular weight of about 20,000 to about 450,000; each A is predominantly a polymerized vinyl aromatic hydrocarbon block having a number average molecular weight of from about 2000 to about 115,000; 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 10% of the original unsaturation. In other embodiments, 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 of 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.

The preparation of various selectively hydrogenated block copolymers of conjugated dienes and vinyl aromatic hydrocarbons which have been grafted with a carboxylic acid reagent is described in a number of patents including U.S. Pat. Nos. 4,578,429; 4,657,970; and 4,795,782, and the disclosures of these patents relating to grafted selectively hydrogenated block copolymers of conjugated dienes and vinyl aromatic compounds, and the preparation of such compounds are hereby incorporated by reference. U.S. Pat. No. 4,795,782 describes and gives examples of the preparation of the grafted block copolymers by the solution process and the melt process. U.S. Pat. No. 4,578,429 contains an example of grafting of Kraton G1652 (SEBS) polymer with maleic anhydride with 2,5-dimethyl-2,5-di(t-butylperoxy) hexane by a melt reaction in a twin screw extruder.

Examples of commercially available maleated selectively hydrogenated copolymers of styrene and butadiene include Kraton FG1901X, FG1921X, and FG1924X, often referred to as maleated selectively hydrogenated SEBS copolymers.

FG1901X contains about 1.7% w bound functionality as succinic anhydride and about 28% w of styrene. FG1921X contains about 1% w of bound functionality as succinic anhydride and 29% w of styrene. FG1924X contains about 13% 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. For example, Quintac 3530 is available from Nippon Zeon and is believed to be a linear styrene-isoprene-styrene block copolymer.

Unsaturated elastomeric polymers and other polymers and copolymers which are not inherently tacky can be rendered tacky when compounded with an external tackifier. Tackifiers, are generally hydrocarbon resins, wood resins, rosins, rosin derivatives, and the like, which when present in concentrations ranging from about 40% to about 90% by weight of the total adhesive composition, or from about 45% to about 85% by weight, impart pressure-sensitive adhesive characteristics to the elastomeric polymer adhesive formulation. Compositions containing less than about 40% by weight of tackifier additive do not generally show sufficient “quickstick,” or initial adhesion, to function as a pressure-sensitive adhesive, and therefore are not inherently tacky. Compositions with too high a concentration of tackifying additive, on the other hand, generally show too little cohesive strength to work properly in most intended use applications of constructions made in accordance with the instant invention.

It is contemplated that any tackifier known by those of skill in the art to be compatible with elastomeric polymer compositions may be used with the present embodiment of the invention. One such tackifier, found useful is Wingtak 10, a synthetic polyterpene resin that is liquid at room temperature, and sold by the Goodyear Tire and Rubber Company of Akron, Ohio. Wingtak 95 is a synthetic tackifier resin also available from Goodyear that comprises predominantly a polymer derived from piperylene and isoprene. Other suitable tackifying additives may include Escorez 1310, an aliphatic hydrocarbon resin, and Escorez 2596, a C₅-C₉(aromatic modified aliphatic) resin, both manufactured by Exxon of Irving, Tex. Of course, as can be appreciated by those of skill in the art, a variety of different tackifying additives may be used to practice the present invention.

In addition to the tackifiers, other additives may be included in the PSAs to impart desired properties. For example, plasticizers may be included, and they are known to decrease the glass transition temperature of an adhesive composition containing elastomeric polymers. An example of a useful plasticizer is Shellflex 371, a naphthenic processing oil available from Shell Lubricants of Texas. Antioxidants also may be included on the adhesive compositions. Suitable antioxidants include Irgafos 168 and Irganox 565 available from Ciba-Geigy, Hawthorne, N.Y. Cutting agents such as waxes and surfactants also may be included in the adhesives.

The pressure sensitive adhesive may be applied from a solvent, emulsion or suspension, or as a hot melt. The adhesive may be applied to the inner surface of the shrink film by any known method. For example, the adhesive may be applied by die coating curtain coating, spraying, dipping, rolling, gravure or flexographic techniques. The adhesive may be applied to the shrink film in a continuous layer, a discontinuous layer or in a pattern. The pattern coated adhesive layer substantially covers the entire inner surface of the film. As used herein, “substantially covers” is intended to mean the pattern in continuous over the film surface, and is not intended to include adhesive applied only in a strip along the leading or trailing edges of the film or as a “spot weld” on the film.

In one embodiment, an adhesive deadener is applied to portions of the adhesive layer to allow the label to adhere to complex shaped articles. In one embodiment, non-adhesive material such as ink dots or microbeads are applied to at least a portion of the adhesive surface to allow the adhesive layer to slide on the surface of the article as the label is being applied and/or to allow air trapped at the interface between the label and the article to escape.

A single layer of adhesive may be used or multiple adhesive layers may be used. Depending on the shrink film used and the article or container to which the label is to be applied, it may be desirable to use a first adhesive layer adjacent to the shrink film and a second adhesive layer having a different composition on the surface to be applied to the article or container for sufficient tack, peel strength and shear strength.

In one embodiment, the pressure sensitive adhesive has sufficient shear or cohesive strength to prevent excessive shrink-back of the label where adhered to the article upon the action of heat after placement of the label on the article, sufficient peel strength to prevent the film from label from lifting from the article and sufficient tack or grab to enable adequate attachment of the label to the article during the labeling operation. In one embodiment, the adhesive moves with the label as the shrink film shrinks upon the application of heat. In another embodiment, the adhesive holds the label in position so that as the shrink film shrinks, the label does not move.

The heat shrinkable film may include other layers in addition to the monolayer or multilayer heat shrinkable polymeric film. In one embodiment, a metalized coating of a thin metal film is deposited on the surface of the polymeric film. The heat shrinkable film may also include a print layer on the polymer film. The print layer may be positioned between the heat shrink layer and the adhesive layer, or the print layer may be on the outer surface of the shrink layer. In one embodiment, the film is reverse printed with a design, image or text so that the print side of the skin is in direct contact with the container to which the film is applied. In this embodiment, the film is transparent.

The labels of the present invention may also contain a layer of an ink-receptive composition that enhances the printability of the polymeric shrink layer or metal layer if present, and the quality of the print layer thus obtained. A variety of such compositions are known in the art, and these compositions generally include a binder and a pigment, such as silica or talc, dispersed in the binder. The presence of the pigment decreases the drying time of some inks. Such ink-receptive compositions are described in U.S. Pat. No. 6,153,288 (Shih et al) and the disclosure of this patent is hereby incorporated by reference.

The print layer may be an ink or graphics layer, and the print layer may be a mono-colored or multi-colored print layer depending on the printed message and/or the intended pictorial design. These include variable imprinted data such as serial numbers, bar codes, trademarks, etc. The thickness of the print layer is typically in the range of about 0.5 to about 10 microns, and in one embodiment about 1 to about 5 microns, and in another embodiment about 3 microns. The inks used in the print layer include commercially available water-based, solvent-based or radiation-curable inks. Examples of these inks include Sun Sheen (a product of Sun Chemical identified as an alcohol dilutable polyamide ink), Suntex MP (a product of Sun Chemical identified as a solvent-based ink formulated for surface printing acrylic coated substrates, PVDC coated substrates and polyolefin films), X-Cel (a product of Water Ink Technologies identified as a water-based film ink for printing film substrates), Uvilith AR-109 Rubine Red (a product of Daw Ink identified as a UV ink) and CLA91598F (a product of Sun Chemical identified as a multibond black solvent-based ink).

In one embodiment, the print layer comprises a polyester/vinyl ink, a polyamide ink, an acrylic ink and/or a polyester ink. The print layer may be formed in the conventional manner by, for example, gravure, flexographic or UV flexographic printing or the like, an ink composition comprising a resin of the type described above, a suitable pigment or dye and one or more suitable volatile solvents onto one or more desired areas of the film. After application of the ink composition, the volatile solvent component(s) of the ink composition evaporate(s), leaving only the non-volatile ink components to form the print layer.

The adhesion of the ink to the surface of the polymeric shrink film or metal layer if present can be improved, if necessary, by techniques well known to those skilled in the art. For example, as mentioned above, an ink primer or other ink adhesion promoter can be applied to the metal layer or the polymeric film layer before application of the ink. Alternatively the surface of the polymeric film can be corona treated or flame treated to improve the adhesion of the ink to the polymeric film layer.

Useful ink primers may be transparent or opaque and the primers may be solvent based or water-based. In one embodiment, the primers are radiation curable (e.g., UV). The ink primer may comprise a lacquer and a diluent. The lacquer may be comprised of one or more polyolefins, polyamides, polyesters, polyester copolymers, polyurethanes, polysulfones, polyvinylidine chloride, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, ionomers based on sodium or zinc salts or ethylene methacrylic acid, polymethyl methacrylates, acrylic polymers and copolymers, polycarbonates, polyacrylonitriles, ethylene-vinyl acetate copolymers, and mixtures of two or more thereof. Examples of the diluents that can be used include alcohols such as ethanol, isopropanol and butanol; esters such as ethyl acetate, propyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as heptane; and mixtures thereof. The ratio of lacquer to diluent is dependent on the viscosity required for application of the ink primer, the selection of such viscosity being within the skill of the art. The ink primer layer may have a thickness of from about 1 to about 4 microns or from about 1.5 to about 3 microns.

A transparent polymer protective topcoat or overcoat layer may be present in the labels of the invention. The protective topcoat or overcoat layer provide desirable properties to the label before and after the label is affixed to a substrate such as a container. The presence of a transparent topcoat layer over the print layer may, in some embodiments provide additional properties such as antistatic properties stiffness and/or weatherability, and the topcoat may protect the print layer from, e.g., weather, sun, abrasion, moisture, water, etc. The transparent topcoat layer can enhance the properties of the underlying print layer to provide a glossier and richer image. The protective transparent protective layer may also be designed to be abrasion resistant, radiation resistant (e.g, UV), chemically resistant, thermally resistant thereby protecting the label and, particularly the print layer from degradation from such causes. The protective overcoat may also contain antistatic agents, or anti-block agents to provide for easier handling when the labels are being applied to containers at high speeds. The protective layer may be applied to the print layer by techniques known to those skilled in the art. The polymer film may be deposited from a solution, applied as a preformed film (laminated to the print layer), etc.

When a transparent topcoat or overcoat layer is present, it may have a single layer or a multilayered structure. The thickness of the protective layer is generally in the range of about 12.5 to about 125 microns, and in one embodiment about 25 to about 75 microns. Examples of the topcoat layers are described in U.S. Pat. No. 6,106,982 which is incorporated herein by reference.

The protective layer may comprise polyolefins, thermoplastic polymers of ethylene and propylene, polyesters, polyurethanes, polyacryls, polymethacryls, epoxy, vinyl acetate homopolymers, co- or terpolymers, ionomers, and mixtures thereof.

The transparent protective layer may contain UV light absorbers and/or other light stabilizers. Among the UV light absorbers that are useful are the hindered amine absorbers available from Ciba Specialty Chemical under the trade designations “Tinuvin”. The light stabilizers that can be used include the hindered amine light stabilizers available from Ciba Specialty Chemical under the trade designations Tinuvin 111, Tinuvin 123, (bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate; Tinuvin 622, (a dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidniethanol); Tinuvin 770 (bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate); and Tinuvin 783. Additional light stabilizers include the hindered amine light stabilizers available from Ciba Specialty Chemical under the trade designation “Chemassorb”, especially Chemassorb 119 and Chemassorb 944. The concentration of the UV light absorber and/or light stabilizer is in the range of up to about 2.5% by weight, and in one embodiment about 0.05% to about 1% by weight.

The transparent protective layer may contain an antioxidant. Any antioxidant useful in making thermoplastic films can be used. These include the hindered phenols and the organo phosphites. Examples include those available from Ciba Specialty Chemical under the trade designations Irganox 1010, Irganox 1076 or Irgafos 168. The concentration of the antioxidant in the thermoplastic film composition may be in the range of up to about 2.5% by weight, and in one embodiment about 0.05% to about 1% by weight.

A release liner may be adhered to the adhesive layer to protect the adhesive layer during transport, storage and handling prior to application of the label to a substrate. The liner allows for efficient handling of an array of individual labels after the labels are die cut and the matrix is stripped from the layer of facestock material and up to the point where the individual labels are dispensed in sequence on a labeling line. The release liner may have an embossed surface and/or have non-adhesive material, such as microbeads or printed ink dots, applied to the surface of the liner.

Process

The process of applying the labels to articles or containers involves non-traditional operations and equipment. The process begins with traditional dispensing equipment that separates the label from the release liner via a peel plate or tip that presents the label with exposed adhesive to the container or article to be decorated. Referring to FIGS. 6A to 6D, the label 62, which has a central portion 61 and a peripheral portion 63 surrounding the central portion and having an outer boundary defined by the label edges, is contacted to the container 60 initially by applying pressure to the label in the central portion. Having the initial tack point(s) 64 located in a more central portion of the label rather than on the leading edge or peripheral portion of the label facilitates a more even distribution of any darts or wrinkles formed between the leading and trailing edges of the applied label. This in turn facilitates removal of the darts or wrinkles with the application of heat.

For those articles having both compound curves and relatively planar regions, the label may be initially contacted with the container not on a compound curve, but closer to or within a relatively planar area of the container surface.

In one embodiment, the label is pre-heated to soften the shrink film and/or activate the adhesive layer.

Pressure is applied to the transferred label with a series of brushes, rollers, wipers, squeegees, pneumatic rollers, or walking beam in a center outward direction, as indicated by arrows 65, to obtain intimate contact between the label and the container or article. This process is referred to herein as “wipe down” of the label. The center to edge wiping motion forces any air trapped beneath the label to the outer edges, as indicated by arrows 66, and creates smaller, more evenly distributed darts at the edges of the label. As the label covers the complex curves of the article, excess label material accumulates in the form of darts, pleats, channeling, bubbling and other application defects generally in the peripheral portion of the label. Heat is applied to at least a portion of the label to fully and smoothly adhere the label to the container as shown in FIG. 6D.

In one embodiment, pressure is applied to the label using a walking beam system equipped with a foam roller or foam covered beam. The foam roller or beam applies downward pressure in the longitudinal direction to the central region of the label and then proceeds to the outer edges of the label, directing any air trapped under the label and the pleats, wrinkles and/or other defects to the outer edges of the label. This embodiment is illustrated in FIG. 7, wherein container 70 having label 71 applied thereto, is positioned on lower foam block 72a of a walking beam. Upper foam block 72b applies downward pressure onto label 71 on container 70 to push air from under the central portion of the label to the periphery of the label as label and container are compressed between the foam blocks of the walking beam.

Once the label is applied and initial wipe down is completed, the excess label material darts and defects are eliminated by heating at least a portion the label to shrink the darts and/or wrinkles. The label may be heated via passage through a heat tunnel, forced air, steam tunnel, direct contact heat pads or forms. In one embodiment, the label is heated to a temperature of at least 40° C. In one embodiment, the label is heated to at least 60° C., or at least 70° C., or at least 80° C.

A subsequent wipe down of the label may be performed to eliminate any remaining darts or wrinkles in the label. Pressure is again applied to the label in a center outward direction to the label. The second wipe down can be performed by a series of rollers, wipers, squeegees, brushes, pneumatic rollers or a walking beam. The subsequent wipe down may be performed concurrently with the application of heat to the label, or subsequent to the application of heat.

When applying the label to an article or container, the label may be initially tacked to the article by applying pressure in a contact region of the label, and then applying pressure across the label in a direction to a first edge of the label. The contact region may be in the center of the label or may be proximate to a second edge of the label opposite to the first edge. For example, initial contact may be made in the center of the label and then pressure is applied in an outward direction to the edges or periphery of the label. Alternatively, initial contact may be made near one edge of the label and then pressure applied across the label to the opposite edge of the label. When applying the label to the article or container, it is desirable to move the excess label material, i.e., the darts or wrinkles, to at least one label edge. The excess material is typically moved in the direction of the compound curve(s), where the heat applied to the label will shrink the label and allow it to conform to the compound curve and eliminate any darts or wrinkles formed. Heat and pressure may be applied to the label simultaneously.

In one embodiment of the invention, the method of applying a label to an article includes the steps of: providing an article having a surface including at least one compound curve; providing a label including (i) a heat shrinkable film having an inner surface and an outer surface; and (ii) a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film, wherein the label has a first edge and a contact region; contacting the adhesive layer in the contact region with the article; and applying heat and pressure simultaneously to the label in a direction from the contact region to the first edge such that the first edge of the label adheres to article and the label shrinks to conform to the compound curve of the article, wherein the heat and pressure are applied by a heated conformable membrane. The contact region may be located in or near the center of the label. Alternatively, the contact region may be proximate to a second edge of the label opposite the first edge.

The heated membrane may, in one embodiment, be pressed against the label on the article or container by a walking beam having a heated bladder. Referring to FIG. 8, the walking beam 80 includes a containment box 82a, 82b on each of its longitudinal members 81a, 81b, the containment box having a flexible and conformable membrane 83a, 83b at its inner surface to create a bladder 87a, 87b. The heated membrane 83a, 83b is positioned onto the passing labeled container 85 via a walking beam mechanism, with the container 85 in a horizontal or vertical position. The membrane may be constructed of a conformable, high temperature, non-porous high-release material. The bladder 87a, 87b is filled with a heated liquid or gas so as to heat the membrane 83a, 83b. The heat from the membrane 83a, 83b is transferred to the label 86 on the container 85. A label may be applied to one or both sides of the container. For the sake of simplicity, a label is applied to only one surface of the container in FIG. 8

In this method, the label 86 is first applied to a center section of the container 85 with a standard peel tip dispensing process (not shown) with leading and trailing edges not tacked down. The labeled container 85 is moved into the walking beam station 80 via a conveyor 84 and the walking beam closes in on one or more containers 85. Pressure from the heated, expanded bladder 87a is applied to the label 86 on the container 85 at an initial contact point in the center of the label in an outward direction to the edges of the label, pushing any air under the label from the center of the label to the outer edges of the label. The bladder is pre-heated to a target temperature based on the line speed and label material used. The heat from the bladder membrane 83a softens the label 86 and shrinks the label. The simultaneous application of heat and pressure from the bladder membrane 83a to the label forces the label to conform to the surface of the container 85, including the compound curve(s) of the container. An optional subsequent heating step may be used to further shrink the label. An advantage of this method is that labels may be applied to a wide variety of container shapes without the need for retooling. In addition, high speed processing is possible due to the continuous heat recovery of the bladder.

FIGS. 9A and 9B illustrate another embodiment of the invention wherein a walking beam with a heated cavity is used to apply the label to the article or container. For illustration purposes, only one side of the walking beam conveyor is shown. The walking beam containment box 90 includes an internally heated bottle-shaped cavity 91. The shape of the cavity 91 is configured to correspond to the container or article 92 to which the label 93 is applied. The cavity is preheated to a target temperature based on the line speed and label material selected. The heated cavity is positioned onto the passing labeled container via a walking beam conveyor. The walking beam may contain a single or multiple cavities for applying heat and pressure to a single or multiple containers. The labeled surface of the container 92 faces the interior of the cavity 91. The interior of the cavity 91 may be lined with a conformable, soft material such as a silicon rubber sheet having imbedded electric heater wires vulcanized in place. Heat and pressure from the cavity 91 softens the label 93 and shrinks the label. Pressure applied by the soft cavity forces air from under the label to the edges of the label to eliminate bubbles. The simultaneous application of heat and pressure from the heated cavity to the label 93 forces the label to conform to the surface of the container, including the compound curve(s) of the container. The excess label material, i.e., darts and wrinkles, are eliminated by the shrinkage of the label. An optional subsequent heating step may be used to further shrink the label. The advantage of this method is that the exact shape of the cavity provides full bottle contact to enable rapid heat transfer and fill pressure to force air out from under the label.

FIG. 10 illustrates another embodiment of the invention for applying labels to a container having compound curves. In this embodiment, a walking beam containment box 100 includes an internally heated soft, flexible pad 101 suspended between at least two frame members 102 as its contact surface. For illustration purposes, only one side of the walking beam conveyor is shown. The heated pad 101 is positioned onto the passing labeled containers via a walking beam conveyor in either the vertical or horizontal direction. The label 104 is first applied to a contact point on the container with a standard peel tip dispensing process (not shown) with the leading and trailing edges of the label not tacked down. The container 103 with the label adhered thereto is moved into the walking beam station via a conveyor and the walking beam moves inward to enclose the container. The heated, flexible pad 101 is positioned to push the label 104 toward the container while removing air from under the label. The pad 101 is pre-heated to a target temperature based on the line speed and label material selected. The heated pad may be porous or non-porous. The simultaneous application of heat and pressure from the heated pad 101 to the label 104 forces the label to conform to the surface of the container, including the compound curve(s) of the container. The heat source may be one or more of radiant electric, IR electric, forced hot air and electric resistance heat integrated with the heated pad. An optional subsequent heating step may be used to further shrink the label. An advantage of this method includes the ability to apply labels to a wide variety of container shapes without the need for retooling.

FIGS. 11A and 11B illustrate another embodiment of the invention wherein a walking beam conveyor includes a rectangular framed containment box 110 having a flexible heated membrane mounted to the rectangular frame. In this embodiment, an extensible, internally heated membrane 111, such as a silicone rubber sheet, is mounted over an open rectangular frame 112 along each side of a walking beam conveyor. For illustration purposes, only one side of the walking beam conveyor is shown. A label may be applied to one or both sides of the container 113. The label 114 is first applied to a contact point on the container with a standard peel tip dispensing process (not shown) with the leading and trailing edges of the label not tacked down. The membrane 111 is mounted so that tension is applied across the membrane. The perimeter dimensions of the rectangular frame 111 are larger than the overall profile of the container 113 to be labeled. In one embodiment, the depth of the frame is greater than one-half the thickness of the container to be labeled to allow the container to penetrate the plane of the membrane. The open/close motion of the walking beam provides sufficient force to trap the container 113 between a supported membrane 111 on each side of the walking beam, or one side of the walking beam, to force the container 113 into the frame 112 while the heated membrane 111 conforms to the surface of the container 113. The membrane is pre-heated to a target temperature based on the line speed and label material selected. The dwell time of the closed walking beam can be controlled through the walking beam station by the design of the cam system. The walking beam may contain a plurality of rectangular frames to apply labels to a plurality of containers. As the walking beam opens and reciprocates, the labeled container may optionally be enclosed within the membranes of the walking beam a second time for a second application of heat and pressure. The simultaneous application of heat and pressure from the membrane 111 to the label 114 forces the label to conform to the surface of the container 113, including the compound curve(s) of the container. An optional subsequent heating step may be used to further shrink the label 114. The advantage of this embodiment is that the generic shape of the rectangular frame allows containers having various shapes to be labeled without the necessity of providing unique frames.

FIGS. 12A and 12B illustrate an embodiment that is similar to that illustrated in FIGS. 11A and 11B. In this embodiment, an extensible, internally heated membrane 121, such as a silicone rubber sheet, is mounted over an open frame 122 along each side of a walking beam conveyor 120. For illustration purposes, only one side of the walking beam conveyor is shown. The dimensions of the frame 121 are configured to correspond to the overall profile of the container 123 to be labeled and are slightly larger to allow space for the membrane as it is pushed into the frame 122. The membrane 121 is mounted so that tension is applied across the membrane. In one embodiment, the depth of the frame is greater than one-half the thickness of the container to be labeled to allow the container to penetrate the plane of the membrane. The open/close motion of the walking beam provides sufficient force to trap the container 123 between a supported membrane 121 on each side of the walking beam, or one side of the walking beam, to force the container 123 into the frame 122 while the heated membrane 121 conforms to the surface of the container 123. The membrane is pre-heated to a target temperature based on the line speed and label material selected. The dwell time of the closed walking beam can be controlled through the walking beam station by the design of the cam system. The walking beam may contain a plurality of shaped frames to apply labels to a plurality of similarly shaped containers. As the walking beam opens and reciprocates, the labeled container may optionally be enclosed within the membranes of the walking beam a second time for a second application of heat and pressure. The simultaneous application of heat and pressure from the membrane 121 to the label 124 forces the label to conform to the surface of the container 123, including the compound curve(s) of the container. An optional subsequent heating step may be used to further shrink the label. An advantage of this embodiment is that the shaped frame enables better conformability to the contours around the top and bottom of the containers.

FIG. 13 illustrates an embodiment of the invention wherein a walking beam includes a flexible porous mesh that is externally heated with hot air. In this embodiment, a walking beam containment box 130 includes an externally heated soft, flexible mesh or fabric 131 suspended between at least two frame members 132 as its contact surface. For illustration purposes, only one side of the walking beam conveyor is shown. The heated mesh is positioned onto the passing labeled containers via a walking beam conveyor in the horizontal direction. The label 136 is first applied to a contact point or region on the container with a standard peel tip dispensing process (not shown) with the leading and trailing edges of the label not tacked down. The container 135 with the label adhered thereto is moved into the walking beam station via a conveyor and the walking beam moves inward to enclose the container. The heated, flexible mesh 131 is positioned to push the label 136 toward the container while removing air from under the label. The mesh 131 is heated to a target temperature with a source of hot air 134 based on the line speed and label material selected. The hot air from the hot air source 134 is blown through the pores 133 of the mesh to heat the label on the container 135. The mesh may be constructed, for example, from a mesh screen, a non-woven fabric or a thin, porous foam sheeting. The simultaneous application of heat and pressure from the heated mesh to the label forces the label to conform to the surface of the container, including the compound curve(s) of the container. An optional subsequent heating step may be used to further shrink the label 136. The advantages of this method include excellent contact with the container and heat transfer from the heated air to the labeled container. This method enables very good recovery of heat and recovery of the shape of the mesh. This embodiment may be used on a variety of container shapes and is able to achieve higher temperatures based on the thermal stability of the mesh material.

FIGS. 14A and 14B illustrate an embodiment of the invention wherein a walking beam 140 includes one or more containment boxes, each having an expandable membrane 142 as its contact surface to create an expandable bladder 143. For illustration purposes, only one side of the walking beam conveyor is shown. The heated membrane 143 is positioned onto the passing labeled container 145 via a walking beam mechanism, with the container 145 in a horizontal or vertical position. The membrane may be constructed of a conformable, high temperature, non-porous high-release material. The bladder 143 is filled with a heated liquid or gas so as to heat the membrane 142. The heat from the membrane 142 is transferred to the label 146 on the container 145. A label may be applied to one or both sides of the container. A label may be applied to one or both sides of the container.

In this method, the label 146 is first applied to a center section of the container 145 with a standard peel tip dispensing process (not shown) with leading and trailing edges not tacked down. The labeled container 145 is moved into the walking beam station 140 via a conveyor and the walking beam closes in on one or more containers 145. Pressure from the heated, expanded bladder 143 is applied to the label 146 on the container 145 at a contact point in the center of the label in an outward direction to the edges of the label, pushing any air under the label from the center of the label to the outer edges of the label. The expandable bladder is pre-heated to a target temperature based on the line speed and label material used. The heat from the bladder membrane 142 softens the label 146 and shrinks the label. The simultaneous application of heat and pressure from the bladder membrane 142 to the label forces the label to conform to the surface of the container, including the compound curve(s) of the container. An optional subsequent heating step may be used to further shrink the label. The advantages of this method include the application of labels to a wide variety of container shapes without the need for retooling. In addition, high speed processing is possible due to the continuous heat recovery of the bladder. Another advantage is that the application of heat and pressure in a center outward direction in both the vertical and horizontal direction assures proper label application without generating label defects. Furthermore, due to the limited number of moving mechanical components, low maintenance is required.

The labeled article of the present invention may be used in a variety of applications, including, but not limited to personal care products, household chemical products, food and beverages, toys, electronics, pharmaceuticals, health care products, industrial products and appliances.

EXAMPLES

The following examples are intended only to illustrate methods and embodiments in accordance with the invention, and as such should not be construed as imposing limitations upon the claims.

Example 1

A pressure sensitive shrink label is constructed from a 3 mil thick low density polyethylene multilayer shrink film designated CorrTuff from Sealed Air. The film is coated with an acrylic emulsion adhesive S692N from Avery Dennison. The adhesive is carried on a paper Glassine BG-40 silicone coated release liner. The label is oversized, having the dimensions of approximately 5×3.5 inches, which is 20% greater than the industry standard recommended label size for the bottle to which the label is applied.

A 15 oz Johnson & Johnson Baby Lotion bottle having compound curves is filled with water, capped and processed through a Label-Aire 9000 series labeler at 100 bottles per minute (BPM). The labeler has dual-feed screws with matched speed top and lower belts with Label-Aire 2115-CD labeler heads with high torque stepper motor drive. The labels are pressed down with a walking beam type wipe down apparatus providing straight out, center outward forces to direct the trapped air beneath the label and resultant dart/pleat defects to the edge of the label. The oversized label as applied to the bottle initially results in unacceptable small darts and pleat defects around the perimeter of the label. The labeled bottle is then processed through a Leister hot forced air, conveyor wipe down system at 100 bpm. High velocity 260° C. hot air heats the bottle and label to 50° C., shrinking and taking up the excess label material darts and pleats down to the bottle surface. The label is wiped down with a walking beam for good label contact. The darts shrink and are easily wiped flat after application of heat.

The finished labeled bottle with larger label area and larger graphics content is smoothly wiped down without the darts, pleats, ridges or wrinkle defects present in typical pressure sensitive oversized labels. The darts do not return upon aging. Table 1 below shows the properties of the label components.

Example 2

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 2 mil thick polypropylene multilayer shrink film designated CZPA 200 from Innovia is applied to the bottle having compound curves. After initial wipe down, medium sized darts are formed. High velocity hot air heats the bottle and label to 100° C. The darts shrink and are easily wiped flat after application of heat. The darts do not return after aging.

Example 3

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 2 mil thick polylactic acid single layer shrink film designated EARTHFIRST PLA from Plastic Suppliers is applied to the bottle having compound curves. After initial wipe down, medium sized darts are formed. High velocity hot air heats the bottle and label to 70° C. The darts shrink and are easily wiped flat after application of heat. The darts do not return after aging.

Comparative Example 4

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 2 mil thick machine direction oriented polypropylene single layer roll-on-shrink-on film from Avery Dennison is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 70° C. The darts formed at the top and bottom of the label shrink upon application of heat and are easily wiped down, while the darts formed at the leading and trailing edges remain. The removed darts do not return upon aging.

Comparative Example 5

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 1.9 mil thick transverse direction oriented polyvinyl chloride single layer film designated Penta Label from Kloeckner is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 60° C. The darts formed at the leading and trailing edges of the label shrink upon application of heat and are easily wiped down, while the darts formed at the top and bottom of the label remain. The removed darts do not return upon aging.

Comparative Example 6

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 2 mil thick transverse direction oriented glycol modified polyethylene terephthalate (PETG) single layer film designated Fusion 1775E from Mitsubishi is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 50° C. The darts formed at the leading and trailing edges of the label shrink upon application of heat and are easily wiped down, while the darts formed at the top and bottom of the label remain. The removed darts do not return upon aging.

Comparative Example 7

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 1.4 mil thick machine direction oriented polyvinyl chloride single layer film designated MF-L243/01 from Kloechner is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 60° C. The film does not conform to the container. Initial wipe down is poor with many darts formed in all directions. The darts and ridges remain after the application of heat and a second wipe down. The film exhibits excessive shrink back.

Comparative Example 8

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 2.0 mil thick polypropylene multilayer film designated BTNY from Vifan is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 100° C. The darts formed do not shrink completely at high temperature and do not entirely wipe down flat. The darts return upon aging.

Comparative Example 9

In accordance with the process described in Example 1, a pressure sensitive shrink label constructed from a 3.4 mil thick medium density polyethylene (MDPE) multilayer film designated PE 85 from Charter Films is applied to the bottle having compound curves. High velocity hot air heats the bottle and label to 100° C. The darts formed do not shrink completely at high temperature and do not entirely wipe down flat. The darts return upon aging.

TABLE 1

Film

Ult Tensile

Ex.
Grade
Polymer
Construction
Process
Suppliers
Gauge
(PSI)

1
CorrTuff
LDPE
single layer
double
Sealed Air
3.0
10,000
MD

bubble

20,000
CD

2
CZPA 200
PP
multi-layer
double
Innovia
2.0
20,000
MD

bubble

22,000
CD

3
EARTHFIRST PLA
Poly
single layer
blown
Plastic Suppliers
2.0
8,000
MD

Lactic

8,000
CD

Acid

Comp.
Med Shrink ROSO Film
PP
single layer
MDO
Avery PPD
2.0
—

4

Comp.
Penta Label 2.0 mil
PVC
single layer
TDO
Kloeckner
1.9
7,200
MD

5
OT-M276/41, 71/9400,

16,900
CD

GLGL

Comp.
Fusion 2.0 mil 1775E
PETG
single layer
TDO
Mitsubishi
2.0
7,250
MD

6

29,000
CD

Comp.
MF-L243/01 WHT
PVC
single layer
MDO
Kloechner
1.4
—

7
03/402-B

Comp.
BTNY
PP
multi-layer
tenter
Vifan
2.0
40,000
MD

8

20,000
CD

Comp.
PE 85
MDPE
multi-layer
blown
Charter Films
3.4
3,000
MD

9

3,500
CD

L&W

Modulus
Stiffness
Shrink:
Shrink:

Ex.
(PSI)
(mN)
MD
TD
Adhesive
Liner

1
30,000
MD
26
MD
40%
(106 C.)
49%
(106 C.)
S692N
BG40

30,000
CD
24
CD
70%
(120 C.)
69%
(120 C.)

glassine

2
100,000
MD
24
MD
10%
(106 C.)
0%
(106 C.)
S692N
1.2 mil

130.000
CD
18
CD
14%
(120 C.)
10%
(120 C.)

PET

3
300,000
MD
44
MD
7%
(106 C.)
12%
(106 C.)
S692N
1.2 mil

300,000
CD
60
CD
8%
(120 C.)
14%
(120 C.)

PET

Comp.
200,000
MD
30
MD
14%
(106 C.)
0%
(106 C.)
S692N
1.2 mil

4
123,000
CD
26
CD
23%
(120 C.)
0%
(120 C.)

PET

Comp.
—
52
MD
4%
(106 C.)
56%
(106 C.)
S692N
BG40

5

36
CD

glassine

Comp.
—
70
MD
6%
(106 C.)
66%
(106 C.)
S692N
BG40

6

30
CD

glassine

Comp.
220,000
MD
—
41%
(106 C.)
0%
(106 C.)
S3506
1.2 mil

7
150,000
CD

45%
(120 C.)
+3%
(120 C.)

PET

Comp.
—
35
MD
2%
(106 C.)
0%
(106 C.)
S692N
BG40

8

65
CD
2%
(120 C.)
2%
(120 C.)

glassine

Comp.
75,000
MD
40
MD
0%
(106 C.)
0%
(106 C.)
S692N
BG40

9
60,000
CD
50
CD
4%
(120 C.)
0%
(120 C.)

glassine

While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be under stood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. A method of applying a label to an article, the method comprising: providing an article having a perimeter and having a surface comprising at least one compound curve;providing a label comprising (i) a heat shrinkable film having an inner surface and an outer surface; and (ii) a layer of pressure sensitive adhesive on the inner surface of the heat shrinkable film, wherein the label has a first edge and a contact region;contacting the adhesive layer in the contact region of the label with the article;applying heat and pressure simultaneously to the label in a direction from the contact region to the first edge such that the first edge of the label adheres to the article and the label shrinks to conform to the compound curve of the article;wherein the label adheres to less than half the perimeter of the article at a given cross-section.
2. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a heated bladder.
3. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a heated cavity wherein the shape of the cavity corresponds to the shape of the article to which the label is applied.
4. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a flexible heated membrane suspended between at least two frame members.
5. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a flexible heated membrane mounted to a rectangular frame.
6. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a flexible heated membrane mounted to a frame having a shape corresponding to the shape of the article to which the label is applied.
7. The method of claim 1 wherein heat and pressure are applied by a walking beam comprising a flexible porous mesh suspended between at least two frame members.
8. The method of claim 1 wherein heat and pressure are applied by a flexible, expandable heated membrane.
9. The method of claim 1 wherein the label is provided with a release liner adhered to the adhesive layer and the method further comprises separating the release liner from the label prior to contacting the label with the article.
10. The method of claim 1 wherein the label is heated to a temperature of at least 40° C.
11. The method of claim 1 wherein the heat shrinkable film comprises a film selected from polyester, polyolefin, polyvinyl chloride, polystyrene, polylactic acid, copolymers thereof and blends thereof.
12. The method of claim 1 wherein the heat shrinkable film comprises a polyolefin.
13. The method of claim 1 wherein the heat shrinkable film comprises a multilayer film having a core layer and at least one skin layer.
14. The method of claim 1 wherein the stiffness of the film is at least 5 mN in the machine direction.
15. The method of claim 1 wherein the label further comprises a print layer between the heat shrinkable film and the adhesive layer, wherein the heat shrinkable film is transparent.
16. The method of claim 1 wherein the label further comprises a print layer on the outer surface of the heat shrinkable film.
17. The method of claim 16 wherein the label further comprises a protective layer overlying the print layer.
18. The method of claim 1 wherein the adhesive layer comprises an emulsion adhesive.
19. The method of claim 1 wherein the adhesive layer comprises a hot melt adhesive.
20. The method of claim 1 wherein the adhesive layer comprises a solvent based adhesive.
21. The method of claim 1 wherein the pressure sensitive adhesive layer is continuous.
22. The method of claim 1 wherein the pressure sensitive adhesive layer is patterned and the pattern substantially covers the inner surface of the film wherein the pattern is continuous over the film surface.
23. The method of claim 1 wherein the label comprises a center and a second edge opposite the first edge, and the contact region is proximate to or in the center of the label.
24. The method of claim 1 wherein the label comprises a second edge opposite the first edge and the contact region is proximate to the second edge of the label.
25. The method of claim 1 wherein heat and pressure is applied by a heated conformable membrane.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of PCT/US08/59397 filed Apr. 4, 2008, which claims priority from provisional applications U.S. Ser. No. 60/910,282 filed Apr. 5, 2007 and U.S. Ser. No. 60/938,019 filed May 15, 2007, the entire disclosures of which are incorporated herein by reference, and is related to co-pending U.S. application Ser. No. 12/237,761 filed on Sep. 25, 2008.

US Referenced Citations (543)

Number	Name	Date	Kind
2356951	Runton et al.	Aug 1944	A
3434902	Bliss	Mar 1969	A
3586580	Dullinger	Jun 1971	A
3718495	Tomita	Feb 1973	A
3769147	Komendat et al.	Oct 1973	A
3802942	Amberg et al.	Apr 1974	A
3823050	La Mers	Jul 1974	A
3834607	Muylle	Sep 1974	A
3884396	Gordon et al.	May 1975	A
3908827	Bemmels et al.	Sep 1975	A
3923198	Brochman	Dec 1975	A
3953635	Dunning	Apr 1976	A
4007067	Dunning	Feb 1977	A
4011122	Ashcroft	Mar 1977	A
4021285	Amberg	May 1977	A
4025381	Amberg	May 1977	A
4139099	Daly et al.	Feb 1979	A
4172163	Magnotta	Oct 1979	A
4188249	Fujio	Feb 1980	A
4198560	Dietrich	Apr 1980	A
4210621	Snover et al.	Jul 1980	A
4214937	Geustsen et al.	Jul 1980	A
4217263	Magnotta	Aug 1980	A
4225049	Inoue	Sep 1980	A
4240854	Massey et al.	Dec 1980	A
4250686	Fujio	Feb 1981	A
4275856	Harvey	Jun 1981	A
4286421	Fujito	Sep 1981	A
4287700	Fujio	Sep 1981	A
4290992	Fujio	Sep 1981	A
4293364	Fujio	Oct 1981	A
4300974	Bauer	Nov 1981	A
4313986	Magnotta	Feb 1982	A
4343856	Goswami et al.	Aug 1982	A
4410011	Andrii et al.	Oct 1983	A
4427744	Hume, III	Jan 1984	A
4486366	Reddy	Dec 1984	A
4497275	Johnson et al.	Feb 1985	A
4511425	Boyd et al.	Apr 1985	A
4518468	Fotland et al.	May 1985	A
4536434	Magnotta	Aug 1985	A
4566933	Crankshaw et al.	Jan 1986	A
4585679	Karabedian	Apr 1986	A
4595544	Maruyama et al.	Jun 1986	A
4629663	Brown et al.	Dec 1986	A
4699842	Jorgensen et al.	Oct 1987	A
4714515	Hoffmann	Dec 1987	A
4732641	Nechay et al.	Mar 1988	A
4735664	Asghar et al.	Apr 1988	A
4801348	Takagaki	Jan 1989	A
4801514	Will et al.	Jan 1989	A
4822631	Beaudet	Apr 1989	A
4831799	Glover et al.	May 1989	A
4832783	Nechay et al.	May 1989	A
4835217	Jorgensen et al.	May 1989	A
4844962	May et al.	Jul 1989	A
4863768	Ishio et al.	Sep 1989	A
4871553	Huhndorff	Oct 1989	A
4872931	Mitchell	Oct 1989	A
4874454	Talalay et al.	Oct 1989	A
4874665	Doheny	Oct 1989	A
4910941	Nagano et al.	Mar 1990	A
4911994	Will et al.	Mar 1990	A
4923557	Dickey	May 1990	A
4924714	Gross	May 1990	A
4950344	Glover et al.	Aug 1990	A
4956963	Johnson	Sep 1990	A
4961978	Doheny, Jr. et al.	Oct 1990	A
4963418	Isaka et al.	Oct 1990	A
4982872	Avery	Jan 1991	A
4983238	Yoshida et al.	Jan 1991	A
4997239	Crisp et al.	Mar 1991	A
5021204	Frost et al.	Jun 1991	A
5022941	Doheny, Jr. et al.	Jun 1991	A
5032477	Will et al.	Jul 1991	A
5043204	Itaba et al.	Aug 1991	A
5069953	Kishikawa et al.	Dec 1991	A
5070680	Nagano	Dec 1991	A
5071167	O'Brien	Dec 1991	A
5091237	Schloegl et al.	Feb 1992	A
5102733	Zawadzki	Apr 1992	A
5111953	Faust et al.	May 1992	A
5132074	Isozaki et al.	Jul 1992	A
5135261	Cusack et al.	Aug 1992	A
5143570	Freedman	Sep 1992	A
5145728	Itaba et al.	Sep 1992	A
5147040	Koike et al.	Sep 1992	A
5158815	Doheny, Jr. et al.	Oct 1992	A
5158836	Schirmer et al.	Oct 1992	A
5164444	Bernard	Nov 1992	A
5167974	Grindrod et al.	Dec 1992	A
5169714	Kondo et al.	Dec 1992	A
5173266	Kenney	Dec 1992	A
5176948	Nguyen et al.	Jan 1993	A
5183841	Bernard	Feb 1993	A
5186782	Freedman	Feb 1993	A
5187235	Bordoloi et al.	Feb 1993	A
5189126	Bernard	Feb 1993	A
5190609	Lin et al.	Mar 1993	A
5196504	Scholz et al.	Mar 1993	A
5212009	Peiffer et al.	May 1993	A
5219666	Schirmer et al.	Jun 1993	A
5221706	Lee et al.	Jun 1993	A
5234733	Schloegl et al.	Aug 1993	A
5234736	Lee	Aug 1993	A
5240989	Bernard et al.	Aug 1993	A
5242650	Rackovan et al.	Sep 1993	A
5245456	Yoshimi et al.	Sep 1993	A
5246762	Namamura	Sep 1993	A
5252155	Nowicki et al.	Oct 1993	A
5262216	Popat et al.	Nov 1993	A
5262251	Will et al.	Nov 1993	A
5264532	Bernard	Nov 1993	A
5290842	Sasaki et al.	Mar 1994	A
5292561	Peiffer et al.	Mar 1994	A
5296081	Morin et al.	Mar 1994	A
5298708	Babu et al.	Mar 1994	A
5300353	Yoshimura et al.	Apr 1994	A
5302402	Dudenhoeffer et al.	Apr 1994	A
5306549	Isozaki et al.	Apr 1994	A
5312712	Will et al.	May 1994	A
5316344	Popat et al.	May 1994	A
5318815	Newing et al.	Jun 1994	A
5322876	Sasaki et al.	Jun 1994	A
5326644	Scholz et al.	Jul 1994	A
5326654	Will et al.	Jul 1994	A
5346259	Mocilnikar et al.	Sep 1994	A
5358804	Will et al.	Oct 1994	A
5366575	Staff et al.	Nov 1994	A
5376394	Dudenhoeffer et al.	Dec 1994	A
5383568	Tusick et al.	Jan 1995	A
5385965	Bernard et al.	Jan 1995	A
5390477	Sowden	Feb 1995	A
5397615	Van Beersel et al.	Mar 1995	A
5403416	Bright et al.	Apr 1995	A
5403454	Taniguchi et al.	Apr 1995	A
5407718	Popat et al.	Apr 1995	A
5407752	Fukuzumi et al.	Apr 1995	A
5411295	Bates et al.	May 1995	A
5417901	Hartman et al.	May 1995	A
5420195	Mayer et al.	May 1995	A
5421932	Fujio	Jun 1995	A
5428209	Babu et al.	Jun 1995	A
5443765	Yoshimura et al.	Aug 1995	A
5443895	Peiffer et al.	Aug 1995	A
5460878	Hostetter	Oct 1995	A
5466499	Takagi et al.	Nov 1995	A
5477192	Black et al.	Dec 1995	A
5478422	Bright et al.	Dec 1995	A
5490658	Coward et al.	Feb 1996	A
5491017	Todt	Feb 1996	A
5492950	Brown et al.	Feb 1996	A
5516393	Freedman	May 1996	A
5536787	Scholz et al.	Jul 1996	A
5536800	Scholz et al.	Jul 1996	A
5544770	Travisano	Aug 1996	A
5558913	Sasaki et al.	Sep 1996	A
5563205	Mayer et al.	Oct 1996	A
5565055	Croci	Oct 1996	A
5585193	Josephy et al.	Dec 1996	A
5593747	Georgelos	Jan 1997	A
5597654	Scholz et al.	Jan 1997	A
5607790	Hughen et al.	Mar 1997	A
5614333	Hughen et al.	Mar 1997	A
5618033	Owen et al.	Apr 1997	A
5623011	Bernard	Apr 1997	A
5653927	Flynn et al.	Aug 1997	A
5663228	Sasaki et al.	Sep 1997	A
5665443	Hata et al.	Sep 1997	A
5683774	Faykish et al.	Nov 1997	A
5688456	Kuriu et al.	Nov 1997	A
5690628	Huskey et al.	Nov 1997	A
5691043	Keller et al.	Nov 1997	A
5705551	Sasaki et al.	Jan 1998	A
5709770	Asghar et al.	Jan 1998	A
5709937	Adams et al.	Jan 1998	A
5712031	Kelch et al.	Jan 1998	A
5713567	Owen et al.	Feb 1998	A
5718958	Scholz et al.	Feb 1998	A
5721041	Baratto	Feb 1998	A
5725966	Abe et al.	Mar 1998	A
5726220	Tokushige et al.	Mar 1998	A
5728440	Good	Mar 1998	A
5728469	Mann et al.	Mar 1998	A
5733615	Rackovan et al.	Mar 1998	A
5741563	Mehta et al.	Apr 1998	A
5747192	Hughen et al.	May 1998	A
5753326	Blackwelder	May 1998	A
5759337	Fujio et al.	Jun 1998	A
5759675	Hamada et al.	Jun 1998	A
5766795	Will et al.	Jun 1998	A
5806153	Dolan et al.	Sep 1998	A
5817426	Spada et al.	Oct 1998	A
5827609	Ercillo et al.	Oct 1998	A
5830571	Mann et al.	Nov 1998	A
5833273	Strenk et al.	Nov 1998	A
5843362	Yoshii et al.	Dec 1998	A
5843549	Mingus	Dec 1998	A
5846451	Nakano et al.	Dec 1998	A
5851610	Ristey et al.	Dec 1998	A
5851615	Kay	Dec 1998	A
5856387	Sasaki et al.	Jan 1999	A
5859116	Shih	Jan 1999	A
5865331	Jacobs	Feb 1999	A
5866634	Tokushige et al.	Feb 1999	A
5869160	Mason et al.	Feb 1999	A
5876816	Freedman	Mar 1999	A
5878554	Loree et al.	Mar 1999	A
5879496	Bright et al.	Mar 1999	A
5884425	Baldwin	Mar 1999	A
5891537	Yoshii et al.	Apr 1999	A
5892892	Popat et al.	Apr 1999	A
5897722	Bright	Apr 1999	A
5900091	Kenney	May 1999	A
5904804	Kouda et al.	May 1999	A
5904973	Coward et al.	May 1999	A
5908694	Makar et al.	Jun 1999	A
5914165	Freedman	Jun 1999	A
5925432	Kian et al.	Jul 1999	A
5935730	Will et al.	Aug 1999	A
5948517	Adamko et al.	Sep 1999	A
5952122	Shacklett, III	Sep 1999	A
5954907	LaRose et al.	Sep 1999	A
5961766	Chang et al.	Oct 1999	A
5972444	Patel et al.	Oct 1999	A
5976691	Noguchi et al.	Nov 1999	A
5982284	Baldwin et al.	Nov 1999	A
5985075	Freedman	Nov 1999	A
5990400	Hoshino et al.	Nov 1999	A
5993961	Ugolick et al.	Nov 1999	A
5998018	Murakami et al.	Dec 1999	A
6004682	Rackovan et al.	Dec 1999	A
6016618	Attia et al.	Jan 2000	A
6016641	Nagano	Jan 2000	A
6025079	Ciocca et al.	Feb 2000	A
6042930	Kelch et al.	Mar 2000	A
6070750	Kubitz	Jun 2000	A
6074747	Scholz et al.	Jun 2000	A
6083338	Scholz et al.	Jul 2000	A
6099927	Freedman	Aug 2000	A
6107411	Toya et al.	Aug 2000	A
6113838	Flynn et al.	Sep 2000	A
6113996	Amon et al.	Sep 2000	A
6127024	Weiss et al.	Oct 2000	A
6150013	Balaji et al.	Nov 2000	A
6156252	Freedman	Dec 2000	A
6165609	Curatolo	Dec 2000	A
6176966	Tsujimoto et al.	Jan 2001	B1
6183862	Ko et al.	Feb 2001	B1
6187432	Krish et al.	Feb 2001	B1
6194501	Okada et al.	Feb 2001	B1
6197419	Hyde et al.	Mar 2001	B1
6209605	Lee et al.	Apr 2001	B1
6210524	Josephy	Apr 2001	B1
6225194	Noguchi et al.	May 2001	B1
6231958	Kim et al.	May 2001	B1
6248427	Ast	Jun 2001	B1
6254712	Enlow et al.	Jul 2001	B1
6270866	Okuda et al.	Aug 2001	B1
6270871	Scholz et al.	Aug 2001	B1
6277740	Goldstein	Aug 2001	B1
6280557	Peloquin et al.	Aug 2001	B1
6284337	Lorimor et al.	Sep 2001	B1
6284338	Bauman et al.	Sep 2001	B1
6293037	Spada et al.	Sep 2001	B1
6294111	Shacklett, III et al.	Sep 2001	B1
6294236	Freedman	Sep 2001	B1
6296129	Kawasaki	Oct 2001	B1
6296732	Enlow et al.	Oct 2001	B1
6299716	Bettinger	Oct 2001	B1
6299956	Freedman	Oct 2001	B1
6299975	Takahira et al.	Oct 2001	B1
6312800	Noguchi et al.	Nov 2001	B1
6322883	Williams	Nov 2001	B1
6325879	Heckman et al.	Dec 2001	B1
6329113	Bourdelais et al.	Dec 2001	B1
6336988	Enlow et al.	Jan 2002	B1
6342281	Hayakawa et al.	Jan 2002	B2
6344269	Makar et al.	Feb 2002	B1
6352768	Hseih et al.	Mar 2002	B1
6358587	Saint et al.	Mar 2002	B1
6372074	Holguin et al.	Apr 2002	B1
6376069	Bilodeau et al.	Apr 2002	B1
6383627	Hashimoto et al.	May 2002	B2
6398892	Noguchi et al.	Jun 2002	B1
6413596	Okuda et al.	Jul 2002	B1
6416858	Ercillo et al.	Jul 2002	B1
6417307	Oi et al.	Jul 2002	B1
6418995	Sadrakula et al.	Jul 2002	B1
6423406	Bilodeau	Jul 2002	B1
6436496	Rackovan et al.	Aug 2002	B1
6436501	Steadman	Aug 2002	B1
6436795	Noguchi et al.	Aug 2002	B2
6461555	Freedman	Oct 2002	B1
6461706	Freedman et al.	Oct 2002	B1
6461707	Scholz et al.	Oct 2002	B1
6485803	Bright	Nov 2002	B1
6489387	Mallya et al.	Dec 2002	B2
6503620	Xie et al.	Jan 2003	B1
6509087	Uehara et al.	Jan 2003	B2
6524669	Ito et al.	Feb 2003	B2
6525129	Su et al.	Feb 2003	B1
6534189	Burns et al.	Mar 2003	B1
6540865	Miekka et al.	Apr 2003	B1
6541098	Venkatasanthanam et al.	Apr 2003	B2
6547887	Ko et al.	Apr 2003	B1
6547912	Enlow et al.	Apr 2003	B2
6553700	Hirayama et al.	Apr 2003	B1
6562402	Scholz et al.	May 2003	B2
6579915	Kroll et al.	Jun 2003	B2
6581972	Nojima et al.	Jun 2003	B2
6602790	Kian et al.	Aug 2003	B2
6616727	Koyama et al.	Sep 2003	B1
6627283	Freedman	Sep 2003	B1
6638582	Uchiyama et al.	Oct 2003	B1
6649259	Hu et al.	Nov 2003	B1
6663928	Ito et al.	Dec 2003	B2
6663947	Freedman et al.	Dec 2003	B2
6680097	Amberger et al.	Jan 2004	B1
6691439	Miyashita et al.	Feb 2004	B1
6702910	Noguchi et al.	Mar 2004	B2
6706355	Holguin et al.	Mar 2004	B2
6709761	Hirose et al.	Mar 2004	B2
6716501	Kovalchuk et al.	Apr 2004	B2
6718223	Iwakata et al.	Apr 2004	B1
6720085	Ito et al.	Apr 2004	B2
6723446	Seta et al.	Apr 2004	B2
6726969	Balaji et al.	Apr 2004	B1
6727970	Grace et al.	Apr 2004	B2
6730253	Etesse	May 2004	B2
6733609	Leonarda van Heck	May 2004	B2
6733870	Enlow et al.	May 2004	B2
6748994	Wien et al.	Jun 2004	B2
6755012	Frankefort	Jun 2004	B2
6762124	Kian et al.	Jul 2004	B2
6765070	Tamura et al.	Jul 2004	B2
6773804	Enlow et al.	Aug 2004	B2
6774036	Goldstein	Aug 2004	B2
6780765	Goldstein	Aug 2004	B2
6786376	Pitzen et al.	Sep 2004	B1
6787208	Galovic	Sep 2004	B2
6808776	Mientus et al.	Oct 2004	B2
6808822	Rajan et al.	Oct 2004	B2
6821592	Rodick	Nov 2004	B2
6823867	Avery et al.	Nov 2004	B2
6824001	Johnson et al.	Nov 2004	B2
6824839	Popat et al.	Nov 2004	B1
6835462	Sun et al.	Dec 2004	B2
6841261	Matsui et al.	Jan 2005	B2
6844391	Iyer et al.	Jan 2005	B1
6846531	Mientus et al.	Jan 2005	B2
6855406	Takayasu et al.	Feb 2005	B2
6856086	Grace et al.	Feb 2005	B2
6867983	Liu et al.	Mar 2005	B2
6872462	Roberts et al.	Mar 2005	B2
6875485	Kanai et al.	Apr 2005	B2
6890400	Scholz et al.	May 2005	B2
6891589	Hata et al.	May 2005	B2
6897151	Winter et al.	May 2005	B2
6908687	Mendes et al.	Jun 2005	B2
6919113	Therrian et al.	Jul 2005	B2
6926339	Gentile	Aug 2005	B2
6926959	Kroll et al.	Aug 2005	B2
6932135	Tabuchi	Aug 2005	B2
6940408	Ferguson et al.	Sep 2005	B2
6951596	Green et al.	Oct 2005	B2
6989418	Ko et al.	Jan 2006	B2
6991828	Husemann et al.	Jan 2006	B2
7014920	Kuiru	Mar 2006	B2
7019067	Holguin et al.	Mar 2006	B2
7051493	Cook et al.	May 2006	B2
7079204	Hata	Jul 2006	B2
7093362	Dallmeyer et al.	Aug 2006	B2
7101437	Boutilier et al.	Sep 2006	B2
7105226	Noguchi et al.	Sep 2006	B2
7130007	Hata et al.	Oct 2006	B2
7138703	Maida et al.	Nov 2006	B2
7156528	Weiss et al.	Jan 2007	B2
7156944	Moeller et al.	Jan 2007	B2
7160949	Ota et al.	Jan 2007	B2
7165888	Rodick	Jan 2007	B2
7166342	Hayakawa et al.	Jan 2007	B2
7168815	Shipman et al.	Jan 2007	B2
7182998	Takagi et al.	Feb 2007	B2
7189462	Matsui et al.	Mar 2007	B2
7193014	Wilkey et al.	Mar 2007	B2
7195822	Hiruma	Mar 2007	B2
7215839	Kawahara et al.	May 2007	B2
7223460	Kwok et al.	May 2007	B2
7232857	Hirasawa	Jun 2007	B2
7236222	Yoda et al.	Jun 2007	B2
7247389	Umeda	Jul 2007	B2
7264852	Koishi et al.	Sep 2007	B2
7273894	Shelby et al.	Sep 2007	B2
7330873	Yoshida et al.	Feb 2008	B2
7344765	Hayakawa et al.	Mar 2008	B2
7351767	Hartsock et al.	Apr 2008	B2
7361390	Yoda et al.	Apr 2008	B2
7365816	Kawai et al.	Apr 2008	B2
7368153	Barmore et al.	May 2008	B2
7388146	Fraas et al.	Jun 2008	B2
7422779	Van Rijn et al.	Sep 2008	B2
7427019	Haertel	Sep 2008	B2
D579344	Kunz	Oct 2008	S
7435456	Nakamura	Oct 2008	B2
7473473	Verrocchi	Jan 2009	B2
7491432	Kachi et al.	Feb 2009	B2
7502088	Suzuki et al.	Mar 2009	B2
7525463	Saunders et al.	Apr 2009	B2
7588807	Hayashi et al.	Sep 2009	B2
7625612	Ohmori et al.	Dec 2009	B2
7638203	Inagaki et al.	Dec 2009	B2
7700189	Amon et al.	Apr 2010	B2
7709417	Yukawa	May 2010	B2
7727620	Yamada et al.	Jun 2010	B2
7749584	Hayakawa et al.	Jul 2010	B2
7846517	McDaniel	Dec 2010	B2
20010007395	Gentile	Jul 2001	A1
20010014492	Noguchi et al.	Aug 2001	A1
20010014729	Hayakawa et al.	Aug 2001	A1
20010038920	Hashimoto et al.	Nov 2001	A1
20010050287	Namba et al.	Dec 2001	A1
20010052385	Enlow et al.	Dec 2001	A1
20020006723	Goldstein	Jan 2002	A1
20020007903	Enlow et al.	Jan 2002	A1
20020016381	Kroll et al.	Feb 2002	A1
20020025432	Noguchi et al.	Feb 2002	A1
20020045055	Ito et al.	Apr 2002	A1
20020056513	Tabuchi	May 2002	A1
20020064611	Kanai et al.	May 2002	A1
20020074078	Van Heck	Jun 2002	A1
20020090502	Ito et al.	Jul 2002	A1
20020098303	Rackovan et al.	Jul 2002	A1
20020098680	Goldstein	Jul 2002	A1
20020119294	Monkarsh et al.	Aug 2002	A1
20020124931	Etesse	Sep 2002	A1
20020136848	Yoshii et al.	Sep 2002	A1
20020150780	Ito et al.	Oct 2002	A1
20020153345	Johnson et al.	Oct 2002	A1
20020157772	Enlow et al.	Oct 2002	A1
20020168453	McCutchan	Nov 2002	A1
20020186120	Tamura et al.	Dec 2002	A1
20020192412	Satani et al.	Dec 2002	A1
20020197499	Hirose et al.	Dec 2002	A1
20030029544	Noguchi et al.	Feb 2003	A1
20030031866	Noguchi et al.	Feb 2003	A1
20030039775	Kong	Feb 2003	A1
20030054164	Zimmermann et al.	Mar 2003	A1
20030054165	Yamanaka et al.	Mar 2003	A1
20030068453	Kong	Apr 2003	A1
20030092267	Kian et al.	May 2003	A1
20030134062	Rajan et al.	Jul 2003	A1
20030143415	Seta et al.	Jul 2003	A1
20030147042	Kawamoto et al.	Aug 2003	A1
20030152792	Takayasu et al.	Aug 2003	A1
20030157354	Van Veghel et al.	Aug 2003	A1
20030170427	Ito et al.	Sep 2003	A1
20030192541	Avery et al.	Oct 2003	A1
20030199604	Kroll et al.	Oct 2003	A1
20030201007	Fraas et al.	Oct 2003	A1
20030203166	Droznek	Oct 2003	A1
20030218274	Boutillier et al.	Nov 2003	A1
20040010257	Cachia et al.	Jan 2004	A1
20040023488	Goldstein	Feb 2004	A1
20040028862	Burwell et al.	Feb 2004	A1
20040038012	Cook et al.	Feb 2004	A1
20040039775	Yoshida et al.	Feb 2004	A1
20040071962	Tanimoto	Apr 2004	A1
20040091625	Winter et al.	May 2004	A1
20040119922	Hata et al.	Jun 2004	A1
20040124661	Gentile	Jul 2004	A1
20040131806	Barmore et al.	Jul 2004	A1
20040142195	Roberts et al.	Jul 2004	A1
20040175520	Van Rijn et al.	Sep 2004	A1
20040180229	Hayakawa et al.	Sep 2004	A1
20040214142	Sutula, Jr.	Oct 2004	A1
20040258938	Yamanaka et al.	Dec 2004	A1
20040263731	Hata et al.	Dec 2004	A1
20040265361	Kuniya et al.	Dec 2004	A1
20050018328	Hata et al.	Jan 2005	A1
20050019514	Takegawa et al.	Jan 2005	A1
20050031860	Okada et al.	Feb 2005	A1
20050095379	Hayakawa et al.	May 2005	A1
20050106342	Dawes et al.	May 2005	A1
20050118406	Shelby et al.	Jun 2005	A1
20050119359	Shelby et al.	Jun 2005	A1
20050151230	Maida et al.	Jul 2005	A1
20050157389	Shipman et al.	Jul 2005	A1
20050157390	Weiss et al.	Jul 2005	A1
20050165164	Moeller et al.	Jul 2005	A1
20050187344	Wilkey et al.	Aug 2005	A1
20050191439	Hirose et al.	Sep 2005	A1
20050196563	Ito et al.	Sep 2005	A1
20050213320	Kazuhiro et al.	Sep 2005	A1
20050274687	McCutchan	Dec 2005	A1
20060019071	Akita	Jan 2006	A1
20060028601	Kawahara et al.	Feb 2006	A1
20060043169	Haertel	Mar 2006	A1
20060057323	Yukawa et al.	Mar 2006	A1
20060062934	Hayashi et al.	Mar 2006	A1
20060066787	Yoda et al.	Mar 2006	A1
20060071826	Saunders et al.	Apr 2006	A1
20060072057	Yano et al.	Apr 2006	A1
20060077320	Hata et al.	Apr 2006	A1
20060089457	Hartsock et al.	Apr 2006	A1
20060115667	Verrocchi et al.	Jun 2006	A1
20060121219	Shelby et al.	Jun 2006	A1
20060132688	Yoda et al.	Jun 2006	A1
20060159878	Wakai et al.	Jul 2006	A1
20060170848	Kawai et al.	Aug 2006	A1
20060177607	Ohmori et al.	Aug 2006	A1
20060186581	Etesse et al.	Aug 2006	A1
20060215079	Suzuki et al.	Sep 2006	A1
20060216435	Nakamura	Sep 2006	A1
20060222874	Umeda	Oct 2006	A1
20060233984	Suzuki et al.	Oct 2006	A1
20060246231	Koishi et al.	Nov 2006	A1
20060275592	Tsuchida et al.	Dec 2006	A1
20060292104	Guskey et al.	Dec 2006	A1
20070004813	Shelby et al.	Jan 2007	A1
20070043169	Kwok et al.	Feb 2007	A1
20070071967	Inagaki et al.	Mar 2007	A1
20010087191	Kaya et al.	Apr 2007
20070087191	Kaya et al.	Apr 2007	A1
20070099017	Hayakawa et al.	May 2007	A1
20070172669	Amon et al.	Jul 2007	A1
20070175574	Crank	Aug 2007	A1
20070212539	Yamada et al.	Sep 2007	A1
20070224345	Metz et al.	Sep 2007	A1
20070240806	Suzuki et al.	Oct 2007	A1
20080017605	Zhang et al.	Jan 2008	A1
20080026170	Yamada et al.	Jan 2008	A1
20080050651	Wakai et al.	Feb 2008	A1
20080057236	Yamada et al.	Mar 2008	A1
20080289986	Goto et al.	Nov 2008	A1
20080314909	Takeo et al.	Dec 2008	A1
20090022916	Yamada et al.	Jan 2009	A1
20090038736	Lorence et al.	Feb 2009	A1
20090042024	Fujii et al.	Feb 2009	A1
20090142456	Segal et al.	Jun 2009	A1
20090202757	Fujio	Aug 2009	A1
20090278187	Toba	Nov 2009	A1
20090313427	Ukai et al.	Dec 2009	A1

Foreign Referenced Citations (548)

Number	Date	Country
1786009	Nov 1971	DE
2627312	Dec 1977	DE
8618893	Dec 1986	DE
8702448	Apr 1987	DE
3543317	Jun 1987	DE
19642110	Apr 1998	DE
10106383	Aug 2002	DE
102004004827	Sep 2005	DE
0050702	Mar 1981	EP
0060667	Sep 1982	EP
0121371	Oct 1984	EP
0187044	Jul 1986	EP
0208261	Jul 1986	EP
0189986	Aug 1986	EP
0210646	Feb 1987	EP
0313406	Apr 1989	EP
0317499	May 1989	EP
0319258	Jun 1989	EP
0326039	Aug 1989	EP
0340579	Nov 1989	EP
0342854	Nov 1989	EP
0395585	Oct 1990	EP
0400456	Dec 1990	EP
0261923	May 1991	EP
0445445	Sep 1991	EP
0448400	Sep 1991	EP
0454333	Oct 1991	EP
0456890	Nov 1991	EP
0460672	Dec 1991	EP
0477944	Apr 1992	EP
0482620	Apr 1992	EP
0510213	Oct 1992	EP
0588456	Mar 1994	EP
0220885	May 1994	EP
0478868	May 1994	EP
0621310	Oct 1994	EP
0628598	Dec 1994	EP
0663285	Jul 1995	EP
0664534	Jul 1995	EP
0667300	Aug 1995	EP
0486690	Nov 1995	EP
0688720	Dec 1995	EP
0570512	Jan 1996	EP
0698424	Feb 1996	EP
0575333	Apr 1996	EP
0730944	Sep 1996	EP
0733459	Sep 1996	EP
0582242	Oct 1996	EP
0616716	Mar 1997	EP
0779911	Jun 1997	EP
0805110	Nov 1997	EP
0578750	Jun 1998	EP
0852240	Jul 1998	EP
0812450	Oct 1998	EP
0884766	Dec 1998	EP
0930322	Jul 1999	EP
0930329	Jul 1999	EP
0785869	Aug 1999	EP
0959447	Nov 1999	EP
0963292	Dec 1999	EP
0979722	Feb 2000	EP
0983138	Mar 2000	EP
0989162	Mar 2000	EP
0999250	May 2000	EP
1019290	Jul 2000	EP
1024162	Aug 2000	EP
1043360	Oct 2000	EP
1055721	Nov 2000	EP
1072632	Jan 2001	EP
0675806	Feb 2001	EP
0858395	Feb 2001	EP
1074593	Feb 2001	EP
1083014	Mar 2001	EP
1083129	Mar 2001	EP
0891255	Jun 2001	EP
1107214	Jun 2001	EP
1116667	Jul 2001	EP
1120352	Aug 2001	EP
1122776	Aug 2001	EP
1124214	Aug 2001	EP
1145846	Oct 2001	EP
1151847	Nov 2001	EP
1157943	Nov 2001	EP
1160272	Dec 2001	EP
1172782	Jan 2002	EP
1176100	Jan 2002	EP
1184167	Mar 2002	EP
1201585	May 2002	EP
1205193	May 2002	EP
1205194	May 2002	EP
1205195	May 2002	EP
1227119	Jul 2002	EP
1234854	Aug 2002	EP
1238916	Sep 2002	EP
1262523	Dec 2002	EP
1270203	Jan 2003	EP
1270652	Jan 2003	EP
1270664	Jan 2003	EP
1275670	Jan 2003	EP
0772521	Apr 2003	EP
1299293	Apr 2003	EP
1304219	Apr 2003	EP
0932654	May 2003	EP
0831994	Aug 2003	EP
1333043	Aug 2003	EP
1336641	Aug 2003	EP
1340609	Sep 2003	EP
1361260	Nov 2003	EP
1391294	Feb 2004	EP
1118885	Mar 2004	EP
1398360	Mar 2004	EP
1179563	May 2004	EP
1418042	May 2004	EP
1426165	Jun 2004	EP
1431782	Jun 2004	EP
1460101	Sep 2004	EP
1464994	Oct 2004	EP
1464995	Oct 2004	EP
1489437	Dec 2004	EP
1491219	Dec 2004	EP
1491581	Dec 2004	EP
1491585	Dec 2004	EP
1505136	Feb 2005	EP
1288249	Mar 2005	EP
1420951	Mar 2005	EP
1514680	Mar 2005	EP
1538554	Jun 2005	EP
1550690	Jul 2005	EP
1566261	Aug 2005	EP
1571639	Sep 2005	EP
1616695	Jan 2006	EP
1368442	Feb 2006	EP
1632343	Mar 2006	EP
1084815	Apr 2006	EP
1646023	Apr 2006	EP
1647847	Apr 2006	EP
1525572	May 2006	EP
1659425	May 2006	EP
1661536	May 2006	EP
1467857	Jun 2006	EP
1684255	Jul 2006	EP
1688233	Aug 2006	EP
1695818	Aug 2006	EP
1698461	Sep 2006	EP
1712352	Oct 2006	EP
1714912	Oct 2006	EP
1723038	Nov 2006	EP
1724740	Nov 2006	EP
1733874	Dec 2006	EP
1737912	Jan 2007	EP
1747882	Jan 2007	EP
1752285	Feb 2007	EP
1862517	May 2007	EP
0854890	Jun 2007	EP
1810822	Jul 2007	EP
1839849	Oct 2007	EP
1862517	Oct 2007	EP
1876019	Jan 2008	EP
1915418	Apr 2008	EP
1537175	May 2008	EP
1692226	Jun 2009	EP
1692217	May 2010	EP
1187382	Sep 1959	FR
2164680	Aug 1973	FR
2023061	Dec 1979	GB
2142900	Jan 1985	GB
2204048	Nov 1988	GB
2310398	Aug 2007	GB
52115855	Sep 1977	JP
55044846	Mar 1980	JP
56078932	Jun 1981	JP
57025349	Feb 1982	JP
57034921	Feb 1982	JP
58005355	Jan 1983	JP
58118207	Jul 1983	JP
58185230	Oct 1983	JP
59-097175	Jun 1984	JP
59145114	Aug 1984	JP
60219030	Nov 1985	JP
62014687	Jan 1987	JP
62-286726	Dec 1987	JP
63122518	May 1988	JP
63-049702	Oct 1988	JP
63-268743	Nov 1988	JP
63-272680	Nov 1988	JP
63272680	Nov 1988	JP
11-68426	Jul 1989	JP
2019230	Jan 1990	JP
4-041902	Feb 1992	JP
4-161324	Jun 1992	JP
5305664	Nov 1993	JP
6122152	May 1994	JP
62-91555	Oct 1994	JP
63-49702	Dec 1994	JP
7-165945	Jun 1995	JP
8-323859	Dec 1996	JP
9-239833	Sep 1997	JP
9-254257	Sep 1997	JP
9-272182	Oct 1997	JP
10-007168	Jan 1998	JP
10-020788	Jan 1998	JP
10-059412	Mar 1998	JP
10-095454	Apr 1998	JP
10-095470	Apr 1998	JP
10-194328	Jul 1998	JP
10-254364	Sep 1998	JP
10-209771	Nov 1998	JP
10-291252	Nov 1998	JP
10-305867	Nov 1998	JP
10-333577	Dec 1998	JP
10-337796	Dec 1998	JP
11-079210	Mar 1999	JP
11-115133	Apr 1999	JP
11-158241	Jun 1999	JP
11-208667	Aug 1999	JP
11-224049	Aug 1999	JP
11-272172	Oct 1999	JP
11-292135	Oct 1999	JP
11-338356	Dec 1999	JP
2000-025112	Jan 2000	JP
2000-029392	Jan 2000	JP
2000-043156	Feb 2000	JP
2000-047770	Feb 2000	JP
2000-053154	Feb 2000	JP
2000-056689	Feb 2000	JP
2000-057399	Feb 2000	JP
2000-142791	May 2000	JP
2000-177763	Jun 2000	JP
2000-212527	Aug 2000	JP
2000-229357	Aug 2000	JP
2000-305460	Nov 2000	JP
2000-305461	Nov 2000	JP
2000-313754	Nov 2000	JP
2000-326934	Nov 2000	JP
2000-335658	Dec 2000	JP
2000-343139	Dec 2000	JP
2001-002014	Jan 2001	JP
2001-004678	Jan 2001	JP
2001-010663	Jan 2001	JP
2001-019017	Jan 2001	JP
2001-051601	Feb 2001	JP
2001-082868	Mar 2001	JP
2001-088839	Apr 2001	JP
2001-125489	May 2001	JP
2001-145985	May 2001	JP
2001-154587	Jun 2001	JP
2001-158408	Jun 2001	JP
2001-171620	Jun 2001	JP
2001-175179	Jun 2001	JP
2001-180622	Jul 2001	JP
2001-196033	Jul 2001	JP
2001-206379	Jul 2001	JP
2001-206407	Jul 2001	JP
2001-215880	Aug 2001	JP
2001-219961	Aug 2001	JP
2001-225855	Aug 2001	JP
2001-236019	Aug 2001	JP
2001-247652	Sep 2001	JP
2001-266806	Sep 2001	JP
2001-271022	Oct 2001	JP
2001-272915	Oct 2001	JP
2001-290425	Oct 2001	JP
2001-294282	Oct 2001	JP
2001-296805	Oct 2001	JP
2001-315260	Nov 2001	JP
2000-347571	Dec 2001	JP
2001-341773	Dec 2001	JP
2001-350411	Dec 2001	JP
2002-001878	Jan 2002	JP
2002-020705	Jan 2002	JP
2002-032024	Jan 2002	JP
2002-036356	Feb 2002	JP
2002-046715	Feb 2002	JP
2002-047358	Feb 2002	JP
2002-059969	Feb 2002	JP
2002-068150	Mar 2002	JP
2002-072890	Mar 2002	JP
2002-080074	Mar 2002	JP
2002-087432	Mar 2002	JP
2002-096863	Apr 2002	JP
2002-120862	Apr 2002	JP
2002-128133	May 2002	JP
2002-132159	May 2002	JP
2002-154506	May 2002	JP
2002-193235	Jul 2002	JP
2002-193321	Jul 2002	JP
2002-196677	Jul 2002	JP
2002-203525	Jul 2002	JP
2002-205712	Jul 2002	JP
2002-205713	Jul 2002	JP
2002-215044	Jul 2002	JP
2002-253894	Sep 2002	JP
2002-208228	Oct 2002	JP
2002-284173	Oct 2002	JP
2002-294392	Oct 2002	JP
2002-308228	Oct 2002	JP
2002-308240	Oct 2002	JP
2002-316360	Oct 2002	JP
2002-326613	Nov 2002	JP
2002-332016	Nov 2002	JP
2002-337880	Nov 2002	JP
2002-337941	Nov 2002	JP
2002-351333	Dec 2002	JP
2002-361741	Dec 2002	JP
2003-020013	Jan 2003	JP
2003-020014	Jan 2003	JP
2003-026127	Jan 2003	JP
2003-029638	Jan 2003	JP
2003-034369	Feb 2003	JP
2003-040219	Feb 2003	JP
2003-043922	Feb 2003	JP
2003-049131	Feb 2003	JP
2003-054520	Feb 2003	JP
2003-054561	Feb 2003	JP
2003-058057	Feb 2003	JP
2003-063536	Mar 2003	JP
2003-095225	Apr 2003	JP
2003-104330	Apr 2003	JP
2003-128021	May 2003	JP
2003-165512	Jun 2003	JP
2003-166133	Jun 2003	JP
2003-175964	Jun 2003	JP
2003-200528	Jul 2003	JP
2003-200529	Jul 2003	JP
2003-205946	Jul 2003	JP
2003-252384	Sep 2003	JP
2003-255839	Sep 2003	JP
2003-261171	Sep 2003	JP
2003-267437	Sep 2003	JP
2003-271062	Sep 2003	JP
2003-280528	Oct 2003	JP
2003-292029	Oct 2003	JP
2003-300516	Oct 2003	JP
2003-305771	Oct 2003	JP
2003-312723	Nov 2003	JP
2003-321055	Nov 2003	JP
2003-335343	Nov 2003	JP
2004-067117	Mar 2004	JP
2004-067189	Mar 2004	JP
2004-106848	Apr 2004	JP
2004-122385	Apr 2004	JP
2004-123213	Apr 2004	JP
2004-147360	May 2004	JP
2004-168350	Jun 2004	JP
2004-170468	Jun 2004	JP
2004-170469	Jun 2004	JP
2004-170715	Jun 2004	JP
2004-196918	Jul 2004	JP
2004-256143	Sep 2004	JP
2004-258115	Sep 2004	JP
2004-302125	Oct 2004	JP
2004-354743	Dec 2004	JP
2005-001729	Jan 2005	JP
2005-004017	Jan 2005	JP
2005-015030	Jan 2005	JP
2005-022089	Jan 2005	JP
2005-029216	Feb 2005	JP
2005-035238	Feb 2005	JP
2005-041552	Feb 2005	JP
2005-041891	Feb 2005	JP
2005-070739	Mar 2005	JP
2005-077677	Mar 2005	JP
2005-082225	Mar 2005	JP
2005-132453	May 2005	JP
2005-139423	Jun 2005	JP
2005-148331	Jun 2005	JP
2005-162262	Jun 2005	JP
2005-173611	Jun 2005	JP
2005-183093	Jul 2005	JP
2005-186991	Jul 2005	JP
2005-193984	Jul 2005	JP
2005-196151	Jul 2005	JP
2005-212226	Aug 2005	JP
2005-219767	Aug 2005	JP
2005-221982	Aug 2005	JP
2005-239246	Sep 2005	JP
2005-239948	Sep 2005	JP
2005-266592	Sep 2005	JP
2005-280727	Oct 2005	JP
2005-280782	Oct 2005	JP
2005-280789	Oct 2005	JP
2000-318105	Nov 2005	JP
2005-313944	Nov 2005	JP
2005-335764	Dec 2005	JP
2005-338304	Dec 2005	JP
2006-001573	Jan 2006	JP
2006-044797	Feb 2006	JP
2006-047499	Feb 2006	JP
2006-056552	Mar 2006	JP
2006-063139	Mar 2006	JP
2006-116874	May 2006	JP
2006-151479	Jun 2006	JP
2006-156755	Jun 2006	JP
2006-159901	Jun 2006	JP
2006-160796	Jun 2006	JP
2006-168753	Jun 2006	JP
2006-169285	Jun 2006	JP
2006-193215	Jul 2006	JP
2006-201534	Aug 2006	JP
2006-213341	Aug 2006	JP
2006-215245	Aug 2006	JP
2006-225009	Aug 2006	JP
2006-240697	Sep 2006	JP
2006-240721	Sep 2006	JP
2006-248539	Sep 2006	JP
2006-256665	Sep 2006	JP
2006-281584	Oct 2006	JP
2006-282246	Oct 2006	JP
2006-337635	Dec 2006	JP
2006-349749	Dec 2006	JP
2007-025174	Feb 2007	JP
2007-112719	May 2007	JP
2007-156928	Jun 2007	JP
2007-156930	Jun 2007	JP
2007-160543	Jun 2007	JP
2007-160544	Jun 2007	JP
2007-191606	Aug 2007	JP
2007-242248	Sep 2007	JP
2007-291342	Nov 2007	JP
2007-311527	Nov 2007	JP
2007-334086	Dec 2007	JP
2008-022250	Jan 2008	JP
2008-106252	May 2008	JP
2009-058687	Mar 2009	JP
2009-058722	Mar 2009	JP
2009-066966	Apr 2009	JP
2009-114380	May 2009	JP
2009-272564	Nov 2009	JP
2009-301393	Dec 2009	JP
WO 9005672	May 1990	WO
WO9208611	May 1992	WO
WO 9211997	Jul 1992	WO
WO 9213923	Aug 1992	WO
WO 9217306	Oct 1992	WO
WO9301251	Jan 1993	WO
WO 9414611	Jul 1994	WO
WO 9515461	Jun 1995	WO
WO 9521775	Aug 1995	WO
WO 9602386	Feb 1996	WO
WO 9607699	Mar 1996	WO
WO 9610274	Apr 1996	WO
WO 9611804	Apr 1996	WO
WO 9627178	Sep 1996	WO
WO 9633864	Oct 1996	WO
WO 9642115	Dec 1996	WO
WO 9707490	Feb 1997	WO
WO 9711115	Mar 1997	WO
WO9713645	Apr 1997	WO
WO 9713645	Apr 1997	WO
WO 9714558	Apr 1997	WO
WO 9729523	Aug 1997	WO
WO 9731076	Aug 1997	WO
WO 9735719	Oct 1997	WO
WO 9814825	Apr 1998	WO
WO 9832786	Jul 1998	WO
WO 9852742	Nov 1998	WO
WO 9856662	Dec 1998	WO
WO 9915599	Apr 1999	WO
WO 9929490	Jun 1999	WO
WO9952788	Oct 1999	WO
WO9967768	Dec 1999	WO
WO 0004396	Jan 2000	WO
WO 0029469	May 2000	WO
WO0061371	Oct 2000	WO
WO 0119598	Mar 2001	WO
WO 0119692	Mar 2001	WO
WO 0138434	May 2001	WO
WO 0155276	Aug 2001	WO
WO 0164435	Sep 2001	WO
WO 0183612	Nov 2001	WO
WO 0187751	Nov 2001	WO
WO 0190227	Nov 2001	WO
WO 0206133	Jan 2002	WO
WO0207631	Jan 2002	WO
WO 0238192	May 2002	WO
WO 0238193	May 2002	WO
WO 0238194	May 2002	WO
WO 0238641	May 2002	WO
WO 02066569	Aug 2002	WO
WO 02072441	Sep 2002	WO
WO 03006229	Jan 2003	WO
WO 03016026	Feb 2003	WO
WO 03016053	Feb 2003	WO
WO 03039775	Feb 2003	WO
WO 03029002	Apr 2003	WO
WO 03033262	Apr 2003	WO
WO 03055937	Jul 2003	WO
WO 03061957	Jul 2003	WO
WO 03073401	Sep 2003	WO
WO 03078152	Sep 2003	WO
WO0047396	Jan 2004	WO
WO 2004012938	Feb 2004	WO
WO 2004013831	Feb 2004	WO
WO 2004014635	Feb 2004	WO
WO 2004018198	Mar 2004	WO
WO 2004018204	Mar 2004	WO
WO 2004022646	Mar 2004	WO
WO 2004033541	Apr 2004	WO
WO 2004071962	Apr 2004	WO
WO 2004052644	Jun 2004	WO
WO 2004094139	Nov 2004	WO
WO 2004110750	Dec 2004	WO
WO 2004112684	Dec 2004	WO
WO 2005045385	May 2005	WO
WO 2005048218	May 2005	WO
WO 2005056292	Jun 2005	WO
WO 2005061595	Jul 2005	WO
WO 2005061596	Jul 2005	WO
WO 2005061628	Jul 2005	WO
WO 2005063485	Jul 2005	WO
WO 2005068521	Jul 2005	WO
WO 2005073468	Aug 2005	WO
WO 2005075296	Aug 2005	WO
WO 2005086122	Aug 2005	WO
WO 2005083000	Sep 2005	WO
WO 2005085381	Sep 2005	WO
WO 2005092721	Oct 2005	WO
WO 2005095106	Oct 2005	WO
WO 2005095381	Oct 2005	WO
WO 2005100498	Oct 2005	WO
WO 2005110746	Nov 2005	WO
WO 2005113699	Dec 2005	WO
WO 2005123525	Dec 2005	WO
WO2005118288	Dec 2005	WO
WO 2006004094	Feb 2006	WO
WO 2006013967	Feb 2006	WO
WO 2006015884	Feb 2006	WO
WO 2006047655	May 2006	WO
WO 2006051628	May 2006	WO
WO 2006051884	May 2006	WO
WO 2006051920	May 2006	WO
WO2006047665	May 2006	WO
WO 2006060766	Jun 2006	WO
WO 2006062742	Jun 2006	WO
WO 2006070933	Jul 2006	WO
WO 2006075634	Jul 2006	WO
WO 2006077845	Jul 2006	WO
WO 2006084214	Aug 2006	WO
WO 2006095730	Sep 2006	WO
WO 2006109662	Oct 2006	WO
WO 2006113488	Oct 2006	WO
WO 2006121118	Nov 2006	WO
WO 2006134647	Dec 2006	WO
WO 2007015244	Feb 2007	WO
WO 2007054661	May 2007	WO
WO 2007069615	Jun 2007	WO
WO 2008044221	Apr 2008	WO
WO2009124228	Jan 2009	WO

Related Publications (1)

	Number	Date	Country
	20090038736 A1	Feb 2009	US

Provisional Applications (2)

	Number	Date	Country
	60910282	Apr 2007	US
	60938019	May 2007	US

Continuation in Parts (1)

	Number	Date	Country
Parent	PCT/US2008/059397	Apr 2008	US
Child	12237737		US

Pressure sensitive shrink label

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Date Issued

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Agents

CPC

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Field of Search

US

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Abstract