Adhesive-backed articles

Abstract
Methods of preparing adhesive-backed articles and methods of applying adhesives backed articles are described. The adhesive-backed articles include a compliant film and a pressure-sensitive adhesive having a microstructured surface opposite the compliant film.
Description
FIELD OF THE INVENTION

The present invention relates to an adhesive-backed article, more particularly to such an adhesive-backed article having an adhesive with a microstructured surface bonded to a compliant film, and even more particularly to channels, with a specific volume per unit area, formed by the microstructured surface in the adhesive which permit the desirable properties of positionability and fluid egress to a periphery of the article without adversely affecting the surface appearance of the film after application onto a substrate.


BACKGROUND OF THE INVENTION

Films are often bonded to substrates utilizing pressure-sensitive adhesives. The films are generally bonded to a variety of different substrates including, for example, surfaces on motor vehicles. The interface between the adhesive and the contact surface of the substrate is important to the performance of the film. The interface between the adhesive and the substrate is affected by several factors. For example, the application may be affected by the type of adhesive used, the size and type of the films utilized, the surface of the substrate upon which the article is applied, the application technique utilized, or combinations thereof.


Adhesive-backed films are often used for decorative purposes. The placement of a film into a specific position prior to the formation of a bond between the adhesive and the substrate is often difficult, but important for aesthetic reasons. Some adhesive-backed articles are unable to slide on the surface of the substrate and will adhere with the slightest contact on the surface of the substrate. Such articles can often be particularly difficult to reapply if they inadvertently adhere to the substrate. The inability to slide the adhesive-backed article in place can adversely affect the positioning of the article or cause damage to the article upon attempted repositioning after adhesion.


The decorative articles also require that the adhesive-backed article be able to evacuate air or other fluids trapped underneath the adhesive during the bonding step. The ability to bleed fluids and eliminate bubbles from underneath the article improves the overall appearance of the article. Additionally, bubbles under a film can adversely affect the adhesive performance of the article.


Thin films are often utilized on surfaces so that the adhesive film blends with the substrate upon which the film is applied. Additionally, thinner films are generally more flexible and therefore suited for application on contoured surfaces. However, the utilization of thin films can create an appearance problem. The thinner films have a tendency to show all surface abnormalities or uneven portions of either the adhesive or the substrate upon which the adhesive-backed article is applied.


SUMMARY OF THE INVENTION

The present invention relates to an adhesive-backed article. The article includes a compliant film with a pressure sensitive adhesive bonded to a lower surface of the film. The pressure sensitive adhesive includes a microstructured surface opposite the compliant film.


In accordance with the present invention, the microstructured surface defines channels in the pressure sensitive adhesive. The channels comprise a volume of at least 1×103 μm3 per any 500 μm diameter circular area in the adhesive. The channels are utilized to create exit pathways for fluid egress to a periphery of the article when the article is applied to a substrate. The adhesive-backed article sufficiently bonds to a substrate as indicated by a wet out value of at least 85%. The channels are substantially undetectable on an upper surface after final application of the article onto a substrate.


In general, the adhesive-backed article of the present invention is positionable over a substrate prior to forceful application of the article onto the substrate. The microstructured surface of the adhesive permits the article to either slide over the surface of a substrate, or be easily removed from the surface of the substrate, until enough pressure is applied to enable a bond between the adhesive and the surface of the substrate. The article of the present invention also enhances the egress of fluid from the interface between the adhesive and the substrate as a bonding force is applied to the article. The microstructured features are particularly suited for applications utilizing thin films, i.e., less than 300 μm.


The channels of the present invention can take various shapes or patterns. The channels are generally formed by structures in the adhesive that create the microstructured surface. The structures may be either placed randomly about the surface of the adhesive or placed in regular patterns.


The microstructured surface can be formed by directly embossing the pressure sensitive adhesive layer with the structures. Alternatively, a liner or backing can be embossed first and then coated with a pressure sensitive adhesive to impart the structures to the adhesive. The film is typically laminated or bonded to a side of the adhesive layer opposite the microstructured features.


It is an advantage to provide an adhesive-backed article that has pathways in the adhesive for fluid egress and permits positioning of the article without adversely affecting the appearance of the article. The channels define pathways to the periphery of the article that permit the flow of fluid trapped between the adhesive and the surface of the substrate. Additionally, the microstructured surface of the present invention enables the positioning of the article onto a substrate. Further, the microstructured adhesive does not result in observable periodic patterns on the exposed surface of the film after application of the article onto a substrate.


For purposes of the present invention, the following terms used in this application are defined as follows:


“microscopic” refers to structures of small enough dimension so as to require an optic aid to the naked eye when viewed from any plane of view to determine its shape. One criterion is found in Modern Optic Engineering by W. J. Smith, McGraw-Hill, 1966, pages 104-105 whereby visual acuity, “ . . . is defined and measured in terms of the angular size of the smallest character that can be recognized.” Normal visual acuity is considered to be when the smallest recognizable letter subtends an angular height of 5 minutes of arc on the retina. At typical working distance of 250 mm (10 inches), this yields a lateral dimension of 0.36 mm (0.0145 inch) for this object;


“microstructure” means the configuration of structures wherein at least 2 dimensions of the structures are microscopic. The topical and/or cross-sectional view of the structures must be microscopic;


“embossable” refers to the ability of a pressure-sensitive adhesive layer or liner to have part of its surface raised in relief, especially by mechanical means;


“wetting” or “wet out” means spreading out over and intimately contacting a surface;


“positionable” or “positionability” refers to those adhesive-backed articles that can easily slide over a substrate without grabbing or bonding to the substrate absent the application of a force, or adhesive-backed articles that upon light force are capable of releasably bonding to a substrate and upon removal retain at least some form of the original microstructured surface;


“release liner”, used interchangeably with the term “liner”, refers to a flexible sheet which after being placed in intimate contact with pressure-sensitive adhesive surface may be subsequently removed without damaging the adhesive coating;


“microstructured liner” refers to a liner with at least one microstructured surface, which is suitable for contact with an adhesive;


“backing” refers to a thin, flexible sheet which, after being placed in intimate contact with pressure-sensitive adhesive can not be subsequently removed without damaging the adhesive coating;


“microstructured backing” refers to a backing with a microstructured surface.


“substrate” refers to a surface to which the pressure-sensitive adhesive coating is applied for an intended purpose;


“tape” refers to a pressure-sensitive adhesive coating applied to a backing.


“inelastic deformation” means the permanent set at a given strain resulting from a film being stretched to 15% under tension and dissipating that tension.


“compliant” refers to a polymeric film that is soft and flexible as well as having sufficient inelastic deformation after being stretched so that once stretched, the film does not recover to its original length;


“bleedability” or “air-bleedability” refers to the egress of fluids, particularly air, from the interface between the adhesive and the surface of the substrate; and


“appearance” means the visual characteristics of the article as viewed from the exposed surface of the film after application of the article onto a substrate.





BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be more fully appreciated with reference to the following drawings in which similar reference numerals designate like or analogous components throughout and in which:



FIG. 1 is an enlarged, fragmentary, cross-sectional view of an adhesive-backed article according to the invention;



FIG. 2
a is a segmented planar view of a microstructured adhesive surface according to the present invention;



FIG. 2
b is a segmented view of the adhesive backed article highlighting the microstructured features of the present invention;



FIG. 3
a is a perspective view of one embodiment of a microstructured feature according to the present invention;



FIG. 3
b is a perspective view of one embodiment of a truncated microstructured feature according to the present invention;



FIG. 4
a is a perspective view of one embodiment showing a double featured microstructured element according to the present invention;



FIG. 4
b is a perspective view of another embodiment showing a double featured microstructured element according to the present invention;



FIG. 5 is a sectional view showing the configuration of a microstructured surface of an adhesive layer;



FIG. 6 is a sectional view showing a second configuration of microstructured surface of an adhesive layer;



FIG. 7 is a sectional view showing an additional configuration of a microstructured surface of an adhesive layer;



FIG. 8 is a perspective view of a release liner suitable for forming a microstructured surface in an adhesive according to the present invention;



FIG. 9 is a graph indicating the surface roughness of the article of the present invention after it is applied onto a substrate; and



FIG. 10 is a graph indicating the surface roughness of a comparative article after it is applied onto a substrate.





DETAILED DESCRIPTION

The present inventive article 10, as depicted in FIG. 1, includes a compliant film 12 having opposing surfaces 14, 16. A pressure sensitive adhesive 18 is bonded to surface 16 of the compliant film 12. The pressure sensitive adhesive 18 includes a surface 20 that can be bonded to a substrate (not shown). The pressure sensitive adhesive 18 includes structures 22 which define channels 24. A release liner 26 is releasably attached to the pressure sensitive adhesive 18. The release liner 26 includes protrusions 28 that are utilized to form corresponding channels 24 and structures 22 in the pressure sensitive adhesive 18. The release liner 26, shown in a partially removed state, is fully detachable and is used to protect the pressure sensitive adhesive prior to application of the article 10 on a substrate.


The article of the present invention is an improvement over structured adhesives that provide some degree of egress for entrapped air. However, certain structured adhesives are not easily positioned on a substrate. Further, the structures often show through the outer surface of the film after forceful application of the article onto the substrate. This is particularly true with thin films that tend to highlight any underlying surface differences. The present invention imparts a microstructured surface which defines channels in a pressure sensitive adhesive with specific rheological characteristics to address the issues associated with conventional adhesive-backed articles. The channels in the adhesive of the present invention have specific dimensions and characteristics to improve the positionability and fluid egress to a periphery of the article. Additionally, the characteristics of the channels render the microstructured surface of the adhesive substantially undetectable to the human eye when viewed from the exposed surface of the article after application.


The compliant film utilized in the present inventive article is generally made of various plastic materials used conventionally by those skilled in the art. Suitable films include, for example, vinyl, polyvinyl chloride, plasticized polyvinyl chloride, polyurethane, polyethylene, polypropylene, fluororesin or the like. The thickness film can vary widely according to a desired application, but is usually within a range from about 300 μm or less, and preferably about 25 μm to about 100 μm.


A specific example of a suitable compliant layer is a plasticized polyvinyl chloride film, and has sufficient inelastic deformation after being stretched so that when stretched, the film does not recover to its original length. Preferably, the film has an inelastic deformation of at least 5% after being stretched once to 115% of their original length. A typical formulation of the vinyl film includes polyvinyl chloride resin, light and/or heat stabilizer(s), plasticizer, and optionally, pigment. The amount of plasticizer is generally less than about 40% by weight, and is preferably composed of polymeric non-migratable plasticizers which are compatible with the vinyl film and provide the necessary flexibility and durability. A suitable plasticizer is a combination of polymeric polyester elastomer and an ethylene vinyl acetate copolymer (such as Elvaloy 742 made by DuPont Co.) soluble in aromatic solvents and present in amounts of about 26 parts and 10 parts, respectively, per 100 parts vinyl resin.


Primers may optionally be used to enhance the bond between the film and the adhesive. The type of primer will vary with the type of film and adhesive used and one skilled in the art can select an appropriate primer. Examples of suitable primers include chlorinated polyolefins, polyamides, and modified polymers disclosed in U.S. Pat. Nos. 5,677,376, 5,623,010; and those disclosed in WO 98/15601 and WO 99/03907, and other modified acrylic polymers. Typically, primers are dispersed into an adequate solvent in very low concentrations, e.g., less that about 5% solids, and coated onto the film, and dried at room or elevated temperatures to form a very thin layer. Typical solvents used may include water, heptane, toluene, acetone, ethyl acetate, isopropanol, and the like, used alone or as blends thereof.


In accordance with the present invention, useful pressure sensitive adhesives include those which are capable of retaining microstructured features on an exposed surface after being embossed with a microstructured molding tool, backing or liner, or after being coated on a microstructured molding tool, backing or liner from which it is subsequently removed. The particular pressure sensitive adhesive selected for a given application is dependent upon the type of substrate the article will be applied onto and the microstructuring method employed in producing the adhesive-backed article. Additionally, useful microstructured pressure sensitive adhesives should be capable of retaining their microstructured surfaces for a time sufficient to allow utilization of the adhesive-backed article.


Any pressure-sensitive adhesive is suitable for the invention. Adhesives are typically selected based upon the type of substrate that they are to be adhered to. Classes of pressure-sensitive adhesives include acrylics, tackified rubber, tackified synthetic rubber, ethylene vinyl acetate, silicone, and the like. Suitable acrylic adhesives are disclosed, for example, in U.S. Pat. Nos. 3,239,478; 3,935,338; 5,169,727; RE 24,906; 4,952,650; and 4,181,752. A preferred class of pressure-sensitive adhesives are the reaction product of at least alkyl acrylate with at least one reinforcing comonomer. Suitable alkyl acrylates are those having a homopolymer glass transition temperature below about −10° C. and include, for example, n-butyl acrylate, 2-ethylhexylacrylate, isoctylacrylate, isononlyl acrylate, octadecyl acrylate and the like. Suitable reinforcing monomers are those having a homopolymer glass transition temperature about −10° C., and include for example, acrylic acid, itaconic acid, isobornyl acrylate, N,N-dimethylacrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, and the like.


The adhesives may be polymers that are dispersed in solvent or water and coated onto the release liner and dried, and optionally crosslinked. If a solventborne or waterborne pressure-sensitive adhesive composition is employed, then the adhesive layer must undergo a drying step to remove all or a majority of the carrier liquid. Additional coating steps may be necessary to achieve a smooth surface. The adhesives may also be hot melt coated onto the liner or microstructured backing. Additionally, monomeric pre-adhesive compositions can be coated onto the liner and polymerized with an energy source such as heat, UV radiation, e-beam radiation.


The thickness of the adhesive is dependent upon several factors, including for example, the adhesive composition, the type of structures used to form the microstructured surface, the type of substrate, and the thickness of the film. Those skilled in the art are capable of adjusting the thickness to address specific application factors. In general, the thickness of the adhesive layer is greater than the height of the structures which comprise the microstructured surface. Preferably, the thickness of the adhesive layer is within a range from about 10 to about 50 μm.


The pressure sensitive adhesive can optionally include one or more additives. Depending on the method of polymerization, the coating method, the end use, etc., additives selected from the group consisting of initiators, fillers, plasticizers, tackifiers, chain transfer agents, fibrous reinforcing agents, woven and non-woven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity enhancing agents, coloring agents, and mixtures thereof can be used.


The pressure sensitive adhesive of the present invention includes a microstructured surface on an exposed surface of the adhesive opposite the compliant film. The microstructured surface defines channels in the adhesive. Channels are continuous open pathways or grooves that extend into the adhesive from the exposed surface. The channels either terminate at the peripheral portion of the adhesive layer or communicate with other channels that terminate at a peripheral portion of the article. Upon application of the article onto a substrate, the pathways provide an egress to a periphery of the article for fluid trapped at the interface between the adhesive and the substrate.


The channels are created to define a specific volume per any given area of the microstructured surface of the adhesive. The minimum volume per unit area of the adhesive ensures adequate egress for fluids at the interface of the substrate and the adhesive. Preferably, the channels define a volume of at least 1×103 μm3 per any 500 μm diameter circular area in a two-dimensional plane of the adhesive. Most preferably, the channels define a volume in the range of above 1.0×103 μm3 to about 1×107 μm3 on any 500 μm diameter circular area.


The channels of the present invention at least partially disappear upon final application of the article, in order to provide a desirable adhesion to the exposed surface of the film. The ability of the channels to at least partially disappear is dependent upon the shape of the channel and the rheology of the adhesive. In accordance with the present invention, the channel's size and dimensions are selected for the specific pressure sensitive adhesive compositions to obtain a result of at least 85% according to the percent wet out test discussed in the “Examples” section below. The proper wet out enables a sufficient seal between the article and the substrate.


The shape of the channels can vary widely according to the processing methods, but each preferably has a V-shaped, U-shaped, rectangular or trapezoidal cross section on observation in a transverse direction. FIGS. 2A and 2B show a segmented view of the inventive article 30 highlighting trapezoidal channels 34 in the adhesive 38. The adhesive-backed article 30 includes film 32 and adhesive 38. The trapezoidal channels 34 and corresponding structures 36 are formed in the adhesive 38. Side walls 35 of the structures 36 define side walls for the channels 34.


The limits of dimensions of the channels can be described by use of the aspect ratio. The aspect ratio is defined as the ratio of the greatest microscopic dimension of the channel parallel to the plane of the continuous layer of adhesive to the greatest microscopic dimension of the channel perpendicular to the plane of the continuous layer of adhesive. The aspect ratio is measured by taking the cross-sectional dimensions of the channel at an angle perpendicular to the wall of the channel. Depending on the specific type of channel, the limits of the aspect ratio would be about 0.1 to about 20. For example, the structures of FIG. 7 would define channels that would have a preferred aspect ratio of about 10 to about 15.


Channels are generally created by embossing or forming a plurality of structures into the adhesive. The structures may be present in either a random array or in regular patterns. Individual structures at least partially define a portion of a channel in the adhesive. Selected patterns could include rectilinear patterns, polar patterns and other conventional regular patterns. A plurality of structures combine to create the continuous channels on the surface of the adhesive.


The shape of the structures formed in the pressure sensitive adhesive to create the microstructured surface can vary. Examples of structure shapes include but are not limited to those selected from the group consisting of hemispheres, prisms (such as square prisms, rectangular prisms, cylindrical prisms and other similar polygonal features), pyramids, or ellipsoids. Combinations of the different structure shapes can be utilized. The preferred shapes include those selected from the group consisting of hemispheres, prisms, and pyramids. Each individual structure should typically have a height of greater than about 3 micrometers but less than the total thickness of the adhesive layer, and preferably about 3 micrometers to about 50 micrometers. Additionally, some of the structures may be truncated to provide a surface for additional structures, to control the contact surface of the adhesives, and to improve the wet out of the adhesive. FIG. 3A illustrates a quadrangle pyramid 40 as an illustration of one embodiment suitable for use with the present invention. FIG. 3B depicts a truncated quadrangle pyramid 41 that may also be embossed in the pressure sensitive adhesive of the invention.


In the adhesive-backed article of the present invention, the regular patterns or groups of structures have a specific shape and a size to achieve the desired performance parameters. Therefore, the structures are arranged at a pitch (average value of a distance between similar structural points of adjacent structures) of about 400 μm or less, and preferably about 300 μm or less. A pitch larger than 400 μm may undesirably result in a pattern of the features appearing on the surface of the film after application, thereby causing deterioration in the quality of the article's appearance.


Double featured structures are an additional embodiment that are suitable for use in the present inventive article. The stacking or use of two structures enhances the positionability of the article by further reducing the initial contacting surface of the adhesive. FIG. 4A illustrates a truncated, quadrangle pyramid 42 having an exposed surface 43. A second quadrangle pyramid 44, having a base 45, is positioned on exposed surface 43. FIG. 4B depicts another embodiment highlighting the double features of the invention. A rectangular feature 46 provides a base 47 for receiving a base 49 of a second smaller rectangular feature 48. In general, the base surface of a second structure is smaller than the exposed surface of the first feature. Additionally, different configurations or shapes may be combined with base structures to achieve the desirable positioning properties for the present invention.


The positionability of the article is affected by the area of the adhesive that initially contacts the substrate. Preferably, the contact area of the microstructured features results in an initial surface contact area of about 60% or less of the total area of the adhesive in the plane parallel to the continuous layer of adhesive. The positionability of the present invention is determined by the test noted in the “Examples” section. Preferably, the article of the present invention exhibits a positionability test rating of 2 or better.



FIGS. 5-7 are utilized to demonstrate the various dimensions and characteristics of the microstructured surface of the pressure sensitive adhesive. The figures represent idealized shapes corresponding to the liner. Those skilled in the art will recognize the pressure sensitive adhesive cannot hold exact tolerances with the scale of the structures utilized in the present invention. FIG. 5 is a segmented perspective view of a pressure sensitive adhesive used in the present invention. The adhesive 50 has a plurality of structures 52. The pitch P between the features 52 is not more than 400 μm. The height h of each feature 52 from the channel 54 is within a range from 3 to 30 μm, the length W1 of the upside of the channel 54 is within a range from 1 μm to the size of the pitch P and furthermore a length W2 of the base of the channel 54 is within a range from 0 μm to the size enough to make a base angle < of the feature to a value within a range from 1 to 90°. The aspect ratio of the corresponding channel would be no greater than 20.



FIG. 6 is an illustration of an adhesive 60 having a truncated structure 62 with a second structure 64 positioned on an upper surface 63 of the truncated structure 62. The pitch P measured from corresponding edges of second structure 64 is not more than 400 μm. The height of each structure from the base of the channel 66 is in a range of about 1 μm to about 30 μm. The length W1 of the upside of the channel 66 is within a range from 1 μm to the size of the pitch P and furthermore a length W2 of the base of the channel 66 is within a range from 0 μm to the size enough to make a base angle α1 of the structure 62 to a value within a range from 1 to 90°. A base angle α2 of the second structure 64 is within a range from 1 to 90°.



FIG. 7 corresponds to the adhesive layer 70 having a microstructured surface 72 in the shape of a quadrangular pyramid. The pitch P between the structures 72 is equal to the length W1 of the upside of the channel 74 and is not more than 400 μm. The height h of each structure 72 from the base of the channel 74 is within a range from 3 to 30 μm. The length W2 of the base of the channel 74 is 0 μm.


The use of a release liner or backing is one method suitable for forming the microstructured adhesive of the present invention. The release liner can be advantageously made of various materials. Preferred materials which the microstructured liner may include, but are not limited to plastics such as polyethylene, polypropylene, polyesters, cellulose acetate, polyvinylchloride, and polyvinylidene fluoride, as well as paper or other substrates coated or laminated with such plastics. These embossable coated papers or thermoplastic films are often siliconized or otherwise treated to impart improved release characteristics. The thickness of the release liner can vary widely according to the desired effect. Furthermore, it is possible to afford structures to the release liner by using various techniques, such as those disclosed in U.S. Pat. No. 5,650,215 (Mazurek), herein incorporated by reference in its entirety.


Suitable release liners as well as adhesive layers on release liners are further described in U.S. application Ser. No. 09/808,636, filed on Mar. 14, 2001 by Fleming et al., herein incorporated by reference in its entirety.



FIG. 8 depicts a liner 80 suitable for creating structures on the surface of an adhesive. The liner 80 includes protrusions 82 that form channels in an adhesive as the adhesive is cast onto the liner.


The article of the present invention is produced by imparting the inventive microstructured surface onto an adhesive with practices conventionally recognized in the art. The features are imparted by embossing the adhesive directly through utilization of molding tools or by coating the adhesive onto a liner or backing previously embossed with the inventive features. Such methods and practices are fully disclosed in U.S. Pat. No. 5,650,215, previously incorporated by reference.


The above-described article can be applied to a variety of substrates, including smooth air-tight surfaces. It is important to match a specific pressure sensitive adhesive to a substrate in order to achieve the desired level of adhesion. Examples of suitable substrates include glass, metal, plastic, wood, and ceramic substrates, and painted surfaces of these substrates. Representative plastic substrates include polyvinyl chloride, ethylene-propylene-diene monomer rubber, polyurethanes, polymethyl methacrylate, engineering thermoplastics (e.g., polyphenylene oxide, polyetheretherketone, polycarbonate), and thermoplastic elastomers. The substrates are generally smooth substrates that accentuate the need for an article with fluid egress. Substrates with rough surface inherently provide an egress for fluids trapped an interface of an applied article because the rough surface permits fluid flow.


The application of the article requires the positioning of the article over the substrate. The microstructured surface of the present invention enable the movement of the adhesive-backed article about the surface of the substrate until pressure is applied to enable adhesive contact and wet out of the adhesive on the surface of the substrate. The appropriate level of pressure and resulting wet out will create a bond between the adhesive and the substrate.


Upon forceful application of the article, the channels permit any entrapped fluid to bleed out around the periphery of the article, thereby eliminating air bubbles. Additionally, the microstructured features of the present invention at least partially collapse during application of the article and thereby increase the amount of adhesive in contact with the substrate. The at least partial disappearance of the channels is indicated through the wet out test, described in the “Examples” below. The present invention demonstrates wet out test results of at least 85%, and preferably at least 95%. The at least partial disappearance of the channels ensures that the article has a desirable level of adhesion to the substrate.


In accordance with the present invention, the microstructured surface of the article is substantially undetectable from the surface of the film and therefore improves the overall appearance of the article. One method for measuring the appearance involves the use of the surface roughness test procedure, fully described in the “Examples” section. The present invention, upon application of the article onto a substrate, exhibit, from the upper surface of the compliant film, an appearance having no periodicity or repetitive pattern. Additionally, the present invention has a surface roughness no greater than the roughness of the film by itself.


The invention will now be described further by way of the following non-limiting examples.


EXAMPLES
Surface Roughness Test

The surface topography of a film is measured using the RST Plus surface profiling system available from Wyko Corporation in the vertical scanning interferometer mode (VSI) at a magnification of 1.2× and a pixel size of 13.64 μm.


The system uses an interference microscope and a computer algorithm to analyze the surface. In the system, a white light beam passes through a microscope objective to the sample surface. A beam splitter reflects half of the incident beam to a reference surface. The beams from the sample and the reference surface recombine at the beam splitter to form interference fringes which are alternating light and dark bands that are visible when the surface is in focus. The reference arm containing the interferometric objective moves vertically to scan the surface at varying heights using a linearized piezoelectric transducer to control the motion. The interference fringes for white light are present only over a very shallow depth for each focus position so the fringe contrast at a single sample point reaches a peak when the point is in focus. The system starts above the focus point and scans the surface at evenly spaced intervals as the camera captures frames of interference data which contain interference signals for each point on the surface. A computer algorithm processes the data to calculate surface heights.


A single line analysis of the surface, such as those indicated in FIGS. 9 and 10, provides a plot of the surface heights along a single line of the sample. The peaks on the plot show whether or not the surface has any periodicity, i.e., a repeating pattern of peaks. The analyses are performed with the tilt term removed to eliminate extraneous data due to the interferometer configuration. The magnification is 1.2× and the pixel size is 13.64 μm. Evidence of periodicity for an adhesive backed film is generally apparent when the roughness of the adhesive-backed film exhibits a surface roughness greater than the surface roughness of the uncoated film. The surface roughness (Ra) is the arithmetic average roughness for the area sampled.


Percent Wetout Test


This technique is used to study the wetting of an adhesive having a microstructured surface onto a smooth transparent substrate. The hardware used with this technique consists of a stereo-microscope (Olympus Model SZH-ZB), a video-camera (Cohu Model 4815) mounted on the microscope, a coaxial vertical illuminator (Olympus Model TL2), and a computer (Hewlett-Packard Vectra QS/20) with a video digitizing board (Imaging Technologies PCVISIONplus) installed which allows the computer to capture and digitize an image. Such an image can subsequently be stored and analyzed by commercial software packages (Jandel JAVA). The coaxial vertical illuminator provides light which is sent through the lens (i.e., the optic axis) to illuminate the subject. This light passes through a circular polarizer mounted on the end of the planar objective lens of the microscope. In practice, the procedure is as follows:

  • 1. Apply the adhesive tape onto a glass (or other optically clear and flat) surface with one pass of a 2 kg roller.
  • 2. Position the laminate so that the adhesive/glass interface is viewed through the glass by a stereo microscope.
  • 3. Adjust the sample so that the glass is perpendicular to the optic axis.
  • 4. Adjust the circular polarizer to optimize light intensity and contrast.
  • 5. Using the image analysis software, capture and digitize the image.
  • 6. Set the software grey value window of acceptance to accept only those grey values (i.e., brightness levels) corresponding to the wet areas.
  • 7. Upon application of the tape, analyze the total wetted area as a percentage of the total imaged area.


    Slide Test for Positionability


A horizontal glass plate, at about 23° C., was cleaned with methyl ethyl ketone


(MEK). A test sample (i.e., pressure sensitive adhesive on the indicated backing), approximately 2.5 cm by 7.5 cm, was draped flat onto the glass plate with the pressure sensitive adhesive side down for approximately 10 seconds. The end edge of the sample was lifted and pulled laterally. The test ratings are as follows:

  • 1. sample slid freely
  • 2. sample slid easily with some resistance
  • 3. sample slid with considerable resistance because of adhesion to the plate, but could be lifted without damage
  • 4. sample stuck to the plate and could not be repositioned without damage


    Volume of Air Channels


The volume of the air channels were calculated based on the sizes of the microstructures in a 500 micrometer diameter circle in the liner. The results are reported in cubic microns per 500 μm circle. The volume of air channels is calculated and indicated in Table 1.


Examples 1-11 and Comparative Examples C1-C5

Embossing rolls were cut with diamond tools or laser machined to provide patterns having varying pitch, depth, widths at the top of the channel and at the base of the channel, and base angles. Polyethylene coated paper release liners having a silicone coating over the polyethylenes, such as those available from Rexam or Inncoat, were embossed between a heated rubber roll and each of the embossing roll to produce microstructured liners with ridges. The rubber roll was heated to a temperature of 110° C. and the polycoated paper was heated to a surface temperature of 110° C. before entering the nip between the rubber roll and the embossing roll. The liners traveled around approximately half of the embossing roll, and then onto a cold can which cooled the liner. The dimensions of the microstructures on the liners are shown in Table 1 and have the shape of inverted square pyramids. The pitch is the distance from one microstructure to the same point on the adjacent microstructure, the height is the height of the microstructure from the base of the channel, W1 is the length of the top of the trapezoidal channel and W2 is the length of the bottom of the trapezoidal channel.


A solvent based acrylic pressure-sensitive adhesive was prepared according to the pressure sensitive adhesive (PSA) copolymer procedure of U.S. Pat. No. 4,737,577, incorporated herein by reference, using 90 parts isooctyl acrylate and 10 parts acrylic acid. The PSA was diluted to about 25% solids with an aziridine crosslinking agent, such as those disclosed in U.S. Pat. No. 5,648,425.


The pressure-sensitive adhesive solution was coated onto the microstructured liners to a dried coating thickness of about 30 micrometers. The solution on each liner was dried at 100° C. for 10 minutes to form an adhesive film having a microstructured surface defining trapezoidal channels with the approximate dimensions calculated from the liner shown in Table 1.


The exposed adhesive side of each example was then laminated at room temperature to a 50 micron thick primed white plasticized flexible and compliant vinyl (PVC) film primed with an acrylic polymer modified with 2-methylaziridine. The primer was an amine functional acrylic polymer in ethyl acetate. The lamination was made using a two roll nip to provide flat pressure-sensitive adhesive coated PVC films. The films were tested for Appearance, Air Bleed Capability, Slidability, and Wet-out according to the above described Test Methods. Test results are shown in Table 1.




















TABLE 1












Avg. Vol. (μm3)







Pitch
Height
W1
W2

per any 500 μm

Air



μm
μm
μm
μm
Angle α1°
circular area
Appearance
Bleedability
Slidability
Wet-out %


























 1
126
16
34
17
62
1.1 × 106
Good
Good
3



 2
198
21
67
3
39
1.1 × 106
Good
Good
3
90.4


 3
198
22
28
3
62
6.1 × 105
Good
Good
3
93.5


 4
197
15
18
1
60
2.8 × 105
Good
Good
3
98.4


 5
200
15
200
0
9
1.9 × 106
Good
Good
2
98.7


 6*
197
25
197
3
28
3.3 × 105
Good
Good
2
99.0


 7
203
20
35
12
60
8.5 × 105
Good
Good
3


 8
297
20
35
12
60
6.0 × 105
Good
Good
3


 9
198
19
38
22
72
9.9 × 105
Good
Good


10
198
19
28
11
71
6.3 × 105
Good
Good


11
197
20
24
1
60
4.8 × 105
Good
Good
3
98.5


C1
1270
22
61
27
52
**
Poor
Good
3


C2
770
20
143
96
40
**
Poor
Good
3


C3
508
20
35
12
60
**
Poor
Good
3





*Includes a secondary feature with a base angle of 60°


**Volume indeterminate within a given 500 μm circle







Examples 1-11, produced in accordance with the present invention, exhibit good appearance, good air bleedability, and at least fair slidability. The appearance was determined by visual examination with the unaided eye. A good appearance result indicates no observable underlying structure. A poor appearance results if the pattern is visible. With respect to Examples C1-C3, the average volume per any 500 μm diameter circular area is indeterminate since some 500 μm diameter circular areas do not have channels. Additionally, Examples C1-C3 have poor appearance indicating that patterns created by the channels are visible with the human eye after application.


Samples from each Example measuring approximately 2.54 cm by 2.54 cm were then laminated to a clean glass plate using a plastic squeegee. The samples were then analyzed for surface roughness and periodicity according to the procedure described above. Example C4 is the vinyl film with no adhesive laminated to it, and C5 is the vinyl film with a non-structured PSA laminated to it. Results are shown in Table 2.












TABLE 2





Ex
Ra Value - μm
Single Line Analysis
PSD


















1
0.99
Irregular peaks, no
No spikes




periodicity



2
0.50
Irregular peaks, no
No spikes




periodicity



5
0.85
Irregular peaks, no
No spikes




periodicity



6
0.54
Irregular peaks,
No spikes




no periodicity



C2
1.60
Definite repeating peaks



C4
1.31
Irregular peaks,





no periodicity



C5
0.65
Irregular peaks,





no periodicity









Examples 1, 2, 5 and 6 have arithmetic average roughness values comparable to that of a vinyl film (Example C5). Example 2, as illustrated in FIG. 9, shows no periodicity or repeating patterns. Example C2 has a higher arithmetic average roughness, but more importantly a repeating pattern or periodicity as indicated by the interferometer data. The periodicity of Example C2, as illustrated in FIG. 10, corresponds to the pitch of the channels in the structured surface of the adhesive. The patterns in C2 are detectable with the human eye. Example C4 has a roughness greater than the vinyl film (Example C5) due to microbubbles present in the adhesive. Examples C4 exhibits no periodicity because the adhesive is not structured.


From the above disclosure of the general principles of the present invention and the preceding detailed description, those skilled in this art will readily comprehend the various modifications to which the present invention is susceptible. Therefore, the scope of the invention should be limited only by the following claims and equivalents thereof.

Claims
  • 1. An adhesive-backed film comprising: a compliant pigmented polymeric film having an upper surface and a lower surface, said compliant film having an inelastic deformation of at least 5 percent after being stretched once to 115 percent of its original length wherein the compliant film is solid; anda pressure sensitive adhesive permanently bonded to the planar lower surface of said compliant polymeric film, said pressure sensitive adhesive having a microstructured surface, opposite said film, that can be bonded to a surface of a motor vehicle, with a pattern of channels being formed in said microstructured surface that define a volume ranging from at least 1×103 μm3 up to about 1×107 μm3 per any 500 μm diameter circular area of said pattern so that, after final application of said article onto the surface of a motor vehicle, the upper surface of said compliant film has an appearance with substantially no periodicity and substantially no surface roughness beyond the periodicity and surface roughness of the film by itself in accordance with the Surface Roughness Test,wherein channels formed on the microstructured surface define exit pathways that provide a fluid egress from behind said article when said article is applied to the surface of a motor vehicle and wherein the adhesive-backed film is suitable for being adhered to a surface of a motor vehicle.
  • 2. The adhesive-backed film according to claim 1, wherein after final application of said adhesive-backed film onto the surface of a motor vehicle, the pattern of said channels is prevented from appearing on the surface of said compliant film.
  • 3. The adhesive-backed film according to claim 1, wherein said compliant film has a thickness of 300 μm or less.
  • 4. The adhesive-backed film according to claim 1, wherein said compliant film has a thickness of about 25 μm to about 100 μm.
  • 5. The adhesive-backed film according to claim 1, wherein said compliant film comprises at least one of the plastic materials from the group consisting of vinyl, polyvinyl chloride, plasticized polyvinyl chloride, polyurethane, polyethylene, polypropylene, or fluororesin.
  • 6. The adhesive-backed film according to claim 1, wherein the average distance between adjacent channels in said pattern is up to 400 μm.
  • 7. The adhesive-backed film according to claim 1, wherein said channels have an aspect ratio in the range of about 0.1 to about 20.
  • 8. The adhesive-backed film according to claim 1, wherein said adhesive-backed article is sealable as indicated by an initial wet out test result of at least 85%.
  • 9. The adhesive-backed film according to claim 1, wherein said channels define exit pathways that provide a fluid egress to a periphery of said adhesive-backed film, when said adhesive-backed film is applied to the surface of a motor vehicle.
  • 10. The adhesive-backed film according to claim 1, wherein said adhesive-backed film is operatively adapted for being adhered to a contoured surface of a motor vehicle.
  • 11. The adhesive-backed film according to claim 1, wherein said pressure sensitive adhesive has a microstructured surface that can be bonded to a contoured surface of a motor vehicle.
  • 12. The adhesive-backed film according to claim 1, wherein the upper surface of said adhesive-backed film has an appearance with substantially no periodicity and substantially no surface roughness beyond the surface roughness of the compliant film by itself in accordance with the Surface Roughness Test, after final application of said adhesive-backed film onto the contoured surface of a motor vehicle.
  • 13. The adhesive-backed film according to claim 1, wherein channels formed on the microstructured surface define exit pathways that provide a fluid egress from behind said adhesive-backed film when said adhesive-backed film is applied to the contoured surface of a motor vehicle.
  • 14. The adhesive-backed film according to claim 1, wherein after final application of said adhesive-backed film onto a contoured surface of a motor vehicle, the pattern of said channels is prevented from appearing on the surface of said compliant film.
  • 15. The adhesive-backed film according to claim 1, wherein said channels define exit pathways that provide a fluid egress to a periphery of said adhesive-backed film, when said adhesive-backed film is applied to the contoured surface of a motor vehicle.
  • 16. The adhesive-backed film of claim 1, wherein the adhesive-backed film has a wet out test result of at least 85%.
  • 17. A method of applying an adhesive-backed film to a surface of a motor vehicle, said method comprising: providing the adhesive-backed film of claim 1;adhering the microstructured surface of the pressure-sensitive adhesive layer to the surface of a motor vehicle,wherein after final application of said adhesive-backed film onto the surface of a motor vehicle, the upper surface of the compliant film has an appearance with substantially no periodicity and substantially no surface roughness beyond the surface roughness of the compliant film by itself in accordance with the Surface Roughness Test.
  • 18. The method according to claim 17, wherein the pressure-sensitive adhesive has an initial wet out test result of at least 85 percent, after said adhering.
  • 19. The method according to claim 17, wherein said adhesive-backed film is adhered to a contoured surface of a motor vehicle.
  • 20. The method according to claim 17, wherein the upper surface of the compliant film has an appearance with substantially no periodicity and substantially no surface roughness beyond the surface roughness of the compliant film by itself in accordance with the Surface Roughness Test, after final application of said adhesive-backed film onto the contoured surface of a motor vehicle.
US Referenced Citations (275)
Number Name Date Kind
1056482 Zoppa Mar 1913 A
1511060 Miller Oct 1924 A
1541311 Anderson Jun 1925 A
2196804 Ball Apr 1940 A
2264628 Engert et al. Dec 1941 A
2555564 Berman Jun 1951 A
2592801 Hanington Apr 1952 A
RE23843 Oace Jun 1954 E
RE23910 Smith Dec 1954 E
RE24906 Ulrich Dec 1960 E
3033702 Fenselau May 1962 A
3036945 Souza May 1962 A
3190178 McKenzie Jun 1965 A
3239478 Harlan, Jr. Mar 1966 A
3301741 Henrickson et al. Jan 1967 A
3314838 Erwin Apr 1967 A
3331729 Danielson et al. Jul 1967 A
3346105 Nye Oct 1967 A
3386846 Zones Jun 1968 A
3409991 Davis et al. Nov 1968 A
3413168 Danielson et al. Nov 1968 A
3554835 Morgan Jan 1971 A
3611919 Thomas Oct 1971 A
3615992 Jeffries Oct 1971 A
3616156 Scholl Oct 1971 A
3635752 Baer et al. Jan 1972 A
3741786 Torney Jun 1973 A
3769114 Weigert Oct 1973 A
3779850 Gerard Dec 1973 A
3802947 McQuade, Jr. Apr 1974 A
3814647 Scher et al. Jun 1974 A
3880953 Downey Apr 1975 A
3887678 Lewicki, Jr. Jun 1975 A
3922435 Asnes Nov 1975 A
3927706 Davey Dec 1975 A
3935338 Robertson Jan 1976 A
3944692 Swenson Mar 1976 A
3953639 Lewicki, Jr. Apr 1976 A
3953692 Amano et al. Apr 1976 A
3989775 Jack et al. Nov 1976 A
3993815 Douek et al. Nov 1976 A
3997702 Schurb et al. Dec 1976 A
4023570 Chinai et al. May 1977 A
4025159 McGrath May 1977 A
4035549 Kennar Jul 1977 A
4037816 Scott Jul 1977 A
4045153 Maurino et al. Aug 1977 A
4053669 Kapasi et al. Oct 1977 A
4054697 Reed et al. Oct 1977 A
4089731 Lewicki, Jr. May 1978 A
4091154 Hirai May 1978 A
4092198 Scher et al. May 1978 A
4109665 Godfrey, Jr. et al. Aug 1978 A
4131663 Lewicki, Jr. Dec 1978 A
4136071 Korpman Jan 1979 A
4151319 Sackoff et al. Apr 1979 A
4158073 Schneider et al. Jun 1979 A
4163822 Walter Aug 1979 A
4166152 Baker et al. Aug 1979 A
4171397 Morrow Oct 1979 A
4181752 Martens et al. Jan 1980 A
4214028 Shortway et al. Jul 1980 A
4219376 Roman Aug 1980 A
4223067 Levens Sep 1980 A
4237889 Gobran Dec 1980 A
4287013 Ronning Sep 1981 A
4288481 Birt et al. Sep 1981 A
4289821 Gray, III et al. Sep 1981 A
4294936 Korpman Oct 1981 A
4320162 Schulz Mar 1982 A
4322450 Gray, III et al. Mar 1982 A
4325768 Schulz Apr 1982 A
4326002 Schulz Apr 1982 A
4329385 Banks et al. May 1982 A
4333980 Russell Jun 1982 A
4340276 Maffitt et al. Jul 1982 A
4343848 Leonard, Jr. Aug 1982 A
4374883 Winslow Feb 1983 A
4376151 Parrotta Mar 1983 A
4377050 Renholts Mar 1983 A
4385951 Pressau May 1983 A
4396448 Ohta et al. Aug 1983 A
4397905 Dettmer et al. Aug 1983 A
4400422 Smith Aug 1983 A
4415615 Esmay et al. Nov 1983 A
4418120 Kealy et al. Nov 1983 A
4427732 Gray, III et al. Jan 1984 A
4430137 Jones Feb 1984 A
4460634 Hasegawa Jul 1984 A
4472480 Olson Sep 1984 A
4517044 Arnold May 1985 A
4518643 Francis May 1985 A
4529654 Drum Jul 1985 A
4539056 Takeshita et al. Sep 1985 A
4544590 Egan Oct 1985 A
4546029 Cancio et al. Oct 1985 A
4546037 King Oct 1985 A
4546900 Lackey Oct 1985 A
4547431 Eckberg Oct 1985 A
4548862 Hartman Oct 1985 A
4551297 Botcher et al. Nov 1985 A
4552615 Amendola et al. Nov 1985 A
4554324 Husman et al. Nov 1985 A
4555284 Quella et al. Nov 1985 A
4556595 Ochi Dec 1985 A
4558258 Miyake Dec 1985 A
4568602 Stow Feb 1986 A
4576850 Martens Mar 1986 A
4587152 Gleichenhagen et al. May 1986 A
4587158 Ewing May 1986 A
4599265 Esmay Jul 1986 A
4605592 Paquette et al. Aug 1986 A
4606962 Reylek et al. Aug 1986 A
4612075 Waugh et al. Sep 1986 A
4615754 Waugh et al. Oct 1986 A
4629663 Brown et al. Dec 1986 A
4630891 Li Dec 1986 A
4637943 Bennett Jan 1987 A
4666751 Pasquali et al. May 1987 A
4693935 Mazurek Sep 1987 A
4702948 Sieber-Gadient Oct 1987 A
4705011 Hibino et al. Nov 1987 A
4713273 Freedman Dec 1987 A
4720325 Rausing et al. Jan 1988 A
4726982 Traynor et al. Feb 1988 A
4728380 Jones et al. Mar 1988 A
4732800 Croshens Mar 1988 A
4735837 Miyasaka et al. Apr 1988 A
4736048 Brown et al. Apr 1988 A
4737112 Jin et al. Apr 1988 A
4737577 Brown Apr 1988 A
4743488 Jones et al. May 1988 A
4761320 Coburn, Jr. Aug 1988 A
4775572 Boberet et al. Oct 1988 A
4777276 Rasmussen et al. Oct 1988 A
4783354 Fagan Nov 1988 A
4814040 Ozawa Mar 1989 A
4818610 Zimmerman et al. Apr 1989 A
4822687 Kessel et al. Apr 1989 A
4855170 Darvell et al. Aug 1989 A
4859512 Jones et al. Aug 1989 A
4861635 Carpenter et al. Aug 1989 A
4873132 Jones et al. Oct 1989 A
4889234 Sorensen et al. Dec 1989 A
4894277 Akasaki Jan 1990 A
4902594 Platzer Feb 1990 A
4908273 Urech et al. Mar 1990 A
4912169 Whitmire et al. Mar 1990 A
4913926 Rutkowski Apr 1990 A
4930266 Calhoun et al. Jun 1990 A
4946527 Battrell Aug 1990 A
4948663 Harter et al. Aug 1990 A
4952650 Young et al. Aug 1990 A
4965113 Jones et al. Oct 1990 A
4968562 Delgado Nov 1990 A
4978565 Pigneul et al. Dec 1990 A
4981544 Nordale Jan 1991 A
4985342 Muramoto et al. Jan 1991 A
4986866 Ohba et al. Jan 1991 A
4988567 Delgado Jan 1991 A
4994322 Delgado et al. Feb 1991 A
5008139 Ochi et al. Apr 1991 A
5017255 Calhoun et al. May 1991 A
5032003 Antes Jul 1991 A
5037680 Papendick et al. Aug 1991 A
5039172 Krieger Aug 1991 A
5051310 Horn et al. Sep 1991 A
5061535 Kreckel et al. Oct 1991 A
5073457 Blackwell Dec 1991 A
5079058 Tomiyama et al. Jan 1992 A
5080957 Leseman et al. Jan 1992 A
5087494 Calhoun et al. Feb 1992 A
5090762 Krieger Feb 1992 A
5091483 Mazurek et al. Feb 1992 A
5122902 Benson Jun 1992 A
5130185 Ness Jul 1992 A
5141740 Rajagopalan et al. Aug 1992 A
5141790 Calhoun et al. Aug 1992 A
5143570 Freedman Sep 1992 A
5145544 Leseman et al. Sep 1992 A
5147698 Cole Sep 1992 A
5154956 Fradrich Oct 1992 A
5158557 Noreen et al. Oct 1992 A
5169704 Faust et al. Dec 1992 A
5169727 Boardman Dec 1992 A
5192612 Otter et al. Mar 1993 A
5194299 Fry Mar 1993 A
5196246 Kauss et al. Mar 1993 A
5203941 Spain et al. Apr 1993 A
5211597 Scott et al. May 1993 A
5227233 Itaba et al. Jul 1993 A
5229186 Tribble et al. Jul 1993 A
5234734 Hamada Aug 1993 A
5246762 Nakamura Sep 1993 A
5250253 Battrell Oct 1993 A
5268228 Orr Dec 1993 A
5273805 Calhoun et al. Dec 1993 A
5278271 Miyajima et al. Jan 1994 A
5296277 Wilson et al. Mar 1994 A
5298791 Liberty et al. Mar 1994 A
5300340 Calhoun et al. Apr 1994 A
5304272 Rohrbacker et al. Apr 1994 A
5310576 Patel et al. May 1994 A
5322731 Callahan, Jr. et al. Jun 1994 A
5338590 Rodriquez Aug 1994 A
5342469 Bodford et al. Aug 1994 A
5344681 Calhoun et al. Sep 1994 A
5344693 Sanders Sep 1994 A
5354597 Capik et al. Oct 1994 A
5362516 Wilson et al. Nov 1994 A
5374468 Babinsky et al. Dec 1994 A
5382464 Ruppel et al. Jan 1995 A
5405675 Sawka et al. Apr 1995 A
5411351 Lasch et al. May 1995 A
5425977 Hopfe Jun 1995 A
5429856 Krueger et al. Jul 1995 A
5437754 Calhoun Aug 1995 A
5449540 Calhoun et al. Sep 1995 A
5455103 Hoagland et al. Oct 1995 A
5458719 Pau et al. Oct 1995 A
5458983 Wang et al. Oct 1995 A
5462765 Calhoun et al. Oct 1995 A
5487929 Rusincovitch et al. Jan 1996 A
5501679 Krueger et al. Mar 1996 A
5506031 Spain et al. Apr 1996 A
5508084 Reeves et al. Apr 1996 A
5529828 Patel et al. Jun 1996 A
5538674 Nisper et al. Jul 1996 A
5582102 Holliday Dec 1996 A
5585178 Calhoun et al. Dec 1996 A
5589246 Calhoun et al. Dec 1996 A
5591290 Walter et al. Jan 1997 A
5599618 Callahan, Jr. et al. Feb 1997 A
5607763 Matsuda Mar 1997 A
5623010 Groves Apr 1997 A
5625006 Callahan, Jr. et al. Apr 1997 A
5639530 Miron et al. Jun 1997 A
5643668 Calhoun et al. Jul 1997 A
5648425 Everaerts et al. Jul 1997 A
5650214 Anderson et al. Jul 1997 A
5650215 Mazurek et al. Jul 1997 A
5665446 Sundet Sep 1997 A
5676787 Rusincovitch et al. Oct 1997 A
5677376 Groves Oct 1997 A
5691034 Krueger et al. Nov 1997 A
5693405 Harvie et al. Dec 1997 A
5698276 Mirabitur Dec 1997 A
5718789 Gebhardt et al. Feb 1998 A
5719247 Delgado et al. Feb 1998 A
5721086 Emslander et al. Feb 1998 A
5787143 Reiss et al. Jul 1998 A
5795636 Keller et al. Aug 1998 A
5800919 Peacock et al. Sep 1998 A
5858160 Piacente et al. Jan 1999 A
5866220 Rusincovitch et al. Feb 1999 A
5871607 Hamilton et al. Feb 1999 A
5889118 Delgado et al. Mar 1999 A
5897930 Calhoun et al. Apr 1999 A
5906883 Blanc-Brude May 1999 A
5958309 Fujii et al. Sep 1999 A
5958447 Haralambopoulos et al. Sep 1999 A
6015606 Abe Jan 2000 A
6060159 Delgado et al. May 2000 A
6074745 Speeney Jun 2000 A
6077560 Moshrefzadeh et al. Jun 2000 A
6083616 Dressler Jul 2000 A
6123890 Mazurek et al. Sep 2000 A
6129971 Brandt et al. Oct 2000 A
6183671 Stauffacher et al. Feb 2001 B1
6197397 Sher et al. Mar 2001 B1
6203885 Sher et al. Mar 2001 B1
6217981 Kanno et al. Apr 2001 B1
6315851 Mazurek et al. Nov 2001 B1
6440880 Mazurek et al. Aug 2002 B2
6911243 Sher et al. Jun 2005 B2
Foreign Referenced Citations (178)
Number Date Country
232709 May 1995 CA
2173855 May 1995 CA
3417746 May 1984 DE
3537433 Oct 1986 DE
4411562 Feb 1995 DE
88301088 Feb 1988 EP
0274875 Jul 1988 EP
0288733 Nov 1988 EP
0336431 Oct 1989 EP
175513 Aug 1990 EP
90312546 Nov 1990 EP
0429269 May 1991 EP
0461796 Dec 1991 EP
276557 Apr 1992 EP
0257984 May 1992 EP
257984 May 1992 EP
0508722 Oct 1992 EP
0529546 Mar 1993 EP
0 279 579 Apr 1993 EP
0539099 Apr 1993 EP
0580981 May 1993 EP
0547593 Jun 1993 EP
0580981 Feb 1994 EP
0313766 Mar 1994 EP
0459059 Jul 1994 EP
609603 Aug 1994 EP
411820 Sep 1994 EP
0336693 Nov 1994 EP
0622431 Nov 1994 EP
0352998 Dec 1994 EP
0507878 Apr 1995 EP
500590 Jul 1995 EP
0529546 Aug 1995 EP
0669350 Aug 1995 EP
0570512 Jan 1996 EP
0479223 Mar 1996 EP
0705894 Apr 1996 EP
444354 May 1996 EP
0570515 Jun 1996 EP
0617708 Sep 1996 EP
439941 Jan 1997 EP
521875 May 1997 EP
0429269 Jul 1997 EP
647256 Apr 1998 EP
0602599 Oct 1998 EP
0784544 Aug 1999 EP
0696603 Oct 1999 EP
0725809 Dec 1999 EP
0572227 Aug 2000 EP
0683216 Aug 2000 EP
1011955 Apr 2003 EP
0752498 Jun 2003 EP
1 511 060 May 1978 GB
1510810 May 1978 GB
1541311 Feb 1979 GB
1543977 Apr 1979 GB
2019315 Oct 1979 GB
2055677 Mar 1981 GB
2290629 Jan 1996 GB
51045137 Apr 1976 JP
52029270 Mar 1977 JP
55129477 Oct 1980 JP
53162156 Mar 1981 JP
57178718 Apr 1982 JP
56074045 Nov 1982 JP
58144187 Aug 1983 JP
59-51966 Mar 1984 JP
59-53787 Mar 1984 JP
5314259 Mar 1984 JP
59044750 Mar 1984 JP
59053787 Mar 1984 JP
59-78285 May 1984 JP
85011156 Mar 1985 JP
60-96444 May 1985 JP
6069623 May 1985 JP
60083829 May 1985 JP
60204643 Oct 1985 JP
61254334 Nov 1986 JP
61293281 Dec 1986 JP
63031734 Feb 1988 JP
63193982 Aug 1988 JP
63223081 Sep 1988 JP
1-256583 Oct 1989 JP
0272328 Mar 1990 JP
90-38574 Aug 1990 JP
2196653 Aug 1990 JP
2229875 Sep 1990 JP
3-67043 Jun 1991 JP
3-243677 Oct 1991 JP
02025229 Oct 1991 JP
3231981 Oct 1991 JP
02075679 Dec 1991 JP
4031478 Feb 1992 JP
04031478 Feb 1992 JP
4043034 Feb 1992 JP
4220480 Aug 1992 JP
3062874 Oct 1992 JP
4301336 Oct 1992 JP
5056938 Mar 1993 JP
0271629 Oct 1993 JP
05254066 Oct 1993 JP
05261867 Oct 1993 JP
5269846 Oct 1993 JP
5271629 Oct 1993 JP
52029271 Oct 1993 JP
0620043 Jan 1994 JP
6-184502 Jul 1994 JP
6184502 Jul 1994 JP
06212131 Aug 1994 JP
06270043 Sep 1994 JP
7029569 Jan 1995 JP
07-090231 Apr 1995 JP
7-138541 May 1995 JP
5309885 May 1995 JP
7-29569 Jun 1995 JP
7-224254 Aug 1995 JP
750303 Sep 1995 JP
7278508 Oct 1995 JP
6193830 Feb 1996 JP
08048951 Feb 1996 JP
2503717 Apr 1996 JP
08100155 Apr 1996 JP
8112305 May 1996 JP
08164580 Jun 1996 JP
8193830 Jul 1996 JP
8225776 Sep 1996 JP
09114383 May 1997 JP
09141812 Jun 1997 JP
09157612 Jun 1997 JP
8000030 Jul 1997 JP
09235525 Sep 1997 JP
09277460 Oct 1997 JP
09309166 Dec 1997 JP
10274940 Oct 1998 JP
2587198 Dec 1998 JP
11-323790 Nov 1999 JP
2001507732 Jun 2001 JP
WO 8504602 Oct 1985 WO
WO 9100945 Jan 1991 WO
WO 9107277 May 1991 WO
WO 9115365 Oct 1991 WO
WO 9205314 Apr 1992 WO
WO 9303107 Feb 1993 WO
WO 9301047 Nov 1993 WO
WO 9400525 Jan 1994 WO
WO 9413465 Jun 1994 WO
WO 9420585 Sep 1994 WO
WO 9511655 May 1995 WO
WO 9511945 May 1995 WO
WO 9533565 Dec 1995 WO
WO 9533575 Dec 1995 WO
WO 9611116 Apr 1996 WO
WO 9615715 May 1996 WO
WO 9632248 Oct 1996 WO
WO 9701776 Jan 1997 WO
WO 9718276 May 1997 WO
WO 9723577 Jul 1997 WO
WO 9725256 Jul 1997 WO
WO 9725268 Jul 1997 WO
WO 9726286 Jul 1997 WO
WO 9731077 Aug 1997 WO
WO 9746631 Dec 1997 WO
WO 9815601 Apr 1998 WO
WO 9816362 Apr 1998 WO
WO 9818878 May 1998 WO
WO 9829516 Jul 1998 WO
WO 9827857 Jul 1998 WO
WO 9829231 Jul 1998 WO
WO 9903907 Jan 1999 WO
WO 9900271 Jan 1999 WO
WO 9903414 Jan 1999 WO
WO 9923020 May 1999 WO
WO 9935201 Jul 1999 WO
WO 9961321 Dec 1999 WO
WO 9965999 Dec 1999 WO
WO 0069985 Nov 2000 WO
WO 0073082 Dec 2000 WO
WO 0073083 Dec 2000 WO
Non-Patent Literature Citations (2)
Entry
Satas, et al., “Handbook of Pressure Sensitive Adhesives”, 2nd Edition, vonNostrand Reinhold, NY, 1989.
Neschen, “An Authority All Around the Picture”, Brochure, Neschen Corporation, 1997.
Related Publications (1)
Number Date Country
20130068367 A1 Mar 2013 US
Divisions (1)
Number Date Country
Parent 11410382 Apr 2006 US
Child 11971980 US
Continuations (2)
Number Date Country
Parent 11971980 Jan 2008 US
Child 13675729 US
Parent 10357151 Feb 2003 US
Child 11410382 US
Continuation in Parts (1)
Number Date Country
Parent 09311101 May 1999 US
Child 10357151 US