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.
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.
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.
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:
a is a segmented planar view of a microstructured adhesive surface according to the present invention;
b is a segmented view of the adhesive backed article highlighting the microstructured features of the present invention;
a is a perspective view of one embodiment of a microstructured feature according to the present invention;
b is a perspective view of one embodiment of a truncated microstructured feature according to the present invention;
a is a perspective view of one embodiment showing a double featured microstructured element according to the present invention;
b is a perspective view of another embodiment showing a double featured microstructured element according to the present invention;
The present inventive article 10, as depicted in
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.
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
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.
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.
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.
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.
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.
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
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:
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:
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.
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.
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.
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
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.
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 |
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 |
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. |
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Number | Date | Country | |
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Parent | 11971980 | Jan 2008 | US |
Child | 13675729 | US | |
Parent | 10357151 | Feb 2003 | US |
Child | 11410382 | US |
Number | Date | Country | |
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Parent | 09311101 | May 1999 | US |
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