Abstract:
A composition that is configured for use in creating a film. The composition includes a vinyl acetate containing polymer, such as a vinyl acetate ethylene (VAE) copolymer, and at least one additive that is a pigment, a surfactant, a dispersant, a wetting agent, a plasticizer, a defoamer, a coupling agent, a solvent, a UV absorber, a fire retardant, or a light stabilizer.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a Continuation-In-Part of International Patent Application No. PCT/US2008/069706 filed on Jul. 10, 2008, which is incorporated herein by reference in its entirety. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to adhesive and non-adhesive articles and methods of making the same. More particularly, the articles, or films, described herein do not contain polyvinyl chloride (“PVC”). The articles can be used in a variety of applications, including for example, signs, graphics, wall covering, pressure sensitive products, and the like. 
       BACKGROUND OF THE INVENTION 
       [0003]    Vinyl films plasticized with plasticizers have been used for many years in adhesive labels, tapes and decorative sheets. Vinyl films, particularly polyvinyl chloride (PVC) films, have had wide acceptance for such applications because, among other things, they are inexpensive and weather resistant and can be colored easily with pigments and dyes. In addition, plasticized polyvinyl chloride (PVC) has had particularly wide acceptance because its properties can be modified over a wide range by the incorporation of plasticizers. These films have been used in various graphic applications with success. 
         [0004]    Although vinyl films have been useful in graphic and wall covering applications because of their superior flexibility and conformability, there is a continuing need to develop films which do not contain PVC. The halogen-containing materials such as PVC have generally been recognized as producing undesirable by-products when burned. 
         [0005]    Accordingly, there is a need for environmentally friendly, non-PVC films that have properties that are comparable with PVC films. The present invention satisfies this need. 
       SUMMARY OF THE INVENTION 
       [0006]    The present invention includes various compositions, films made from the compositions, film laminates and related methods. An exemplary embodiment is a composition that is configured for use in creating films. The composition includes vinyl acetate containing polymer and at least one additive that is a pigment, a surfactant, a dispersant, a wetting agent, a plasticizer, a defoamer, a coupling agent, a solvent, a UV absorber, a fire retardant, or a light stabilizer. A vinyl acetate containing polymer refers to vinyl acetate copolymer or homopolymer or the mixture of the two. An exemplary vinyl acetate copolymer is Vinyl Acetate Ethylene (VAE) Copolymer. The Vinyl Acetate Ethylene (VAE) Copolymer is a product based on the copolymerization of vinyl acetate and ethylene in which the vinyl acetate content can range between 60-95%, and the ethylene content ranges between 5-40% of the total formulation. This product should not be confused with the ethylene vinyl acetate (EVA) copolymers in which the vinyl acetate generally range in composition from 10-40%, and ethylene can vary between 60-90% of the formulation. VAEs are water-based emulsions, whereas EVAs are solid materials used for hot melt and plastic molding applications. VAEs are also sold in powder form, a technology pioneered in Europe. 
         [0007]    Another exemplary embodiment of the invention includes composition comprising: an acrylic copolymer, a VAE copolymer, and additives, e.g., titanium dioxide, surfactant, dispersant, wetting agent, or defoamer. Another exemplary embodiment of the invention includes composition comprising: a hybrid of an acrylic and a VAE copolymer, and additives, e.g., titanium dioxide, surfactant, dispersant, wetting agent, or defoamer. A hybrid of an acrylic and a VAE copolymer refers to a polymer product made by seeded emulsion polymerization where an acrylic monomer is polymerized in the presence of VAE copolymer emulsion as seed latex. Another exemplary embodiment of the invention includes composition comprising: an acrylic copolymer, titanium dioxide, and additives, e.g., surfactant, dispersant, a wetting agent or defoamer. Another exemplary embodiment includes polyurethane, a blend of polyurethane and VAE copolymer, a polyurethane acrylic copolymer, a blend of polyurethane and acrylic copolymer. 
         [0008]    In another embodiment, latex or CaCO 3  (calcium carbonate) can be used instead of titanium dioxide thereby making the film with same or similar opacity, but reducing the cost of the film. In one embodiment, the composition is a liquid formulation. In another embodiment, the composition is an emulsion. 
         [0009]    Another exemplary embodiment is a film including a vinyl acetate containing polymer and at least one additive that is a pigment, a surfactant, a dispersant, a wetting agent, a plasticizer, a defoamer, a coupling agent, a solvent, a UV absorber, a fire retardant, or a light stabilizer. The film has an elongation of at least about 50%. 
         [0010]    Another exemplary embodiment is a film including an acrylic copolymer, VAE, titanium dioxide, and at least one additive that is a surfactant, a dispersant, a wetting agent, or a defoamer. 
         [0011]    Another exemplary embodiment is a film that includes a liner, a pressure sensitive adhesive, a strengthening layer, and a print receptive layer. The print receptive layer includes a material that is an emulsion of a blend of vinyl acetate with VAE, a VAE/acrylic hybrid, a VAE copolymer, or an acrylic formulation. In a further embodiment, the film is a graphics film. 
         [0012]    Another exemplary embodiment is an assembly that includes a liner, a pressure sensitive adhesive, and a strengthening layer that includes a material that is a blend of cross linkable vinyl acetate copolymer with a VAE emulsion, or a polyurethane emulsion, or a blend of polyurethane containing emulsions. 
         [0013]    One exemplary method of making the film of the present invention includes the steps of: making a composition comprising polyvinyl acetate homopolymer or copolymer, titanium dioxide, and additives; and applying the composition as a coat over a liner. The coated liner is then dried and the film peeled from the liner. In another exemplary embodiment of making the film, the composition is cast onto a polyethylene terephthalate (“PET”) film. 
         [0014]    Another exemplary method according to the invention is a method of making a film. The method includes providing components and a substrate, blending the components to form a composition, and coating the substrate with the composition. The composition includes a vinyl acetate containing polymer, and at least one additive that is a pigment, a surfactant, a dispersant, a wetting agent, a plasticizer, a defoamer, a coupling agent, a solvent, a UV absorber, a fire retardant, or a light stabilizer. In other, more detailed features of the invention, the method further includes drying the composition, and removing the dried composition from the substrate. According to a further aspect of the invention, the substrate can be a polyethylene terephthalate film. 
         [0015]    The films of the present invention when tested for tensile strength and tensile elongation, printability by direct printing (non-impact printing) on the film specimen using solvent-based ink-jet printer, and durability in accordance with the procedures of SAE Technical Standard J1960 (Rev. October 2004) exhibit at least one of the following physical properties: tensile elongation at break of at least 100%, good printing without smudges and diffusion of ink as determined by visual inspection, and durability of 1 month to 7 years. 
         [0016]    The non-PVC films of the present invention are weather resistant and can be colored easily with pigments and dyes. In addition, opacity can be modified by adding appropriate amount of pigments. These pigments can be included as a layer, or layers, in the film. Also, a white or gray ink wash can be used to improve the opacity of the film. The non-PVC films can be used in the manufacture of both pressure sensitive adhesive products and non-adhesive sheets and films, which include labels, tapes, banners, signage, vehicle wraps, advertising panels, and decorative sheets, and for a variety of other applications, including but not limited to applications where PVC films are generally used. 
         [0017]    Other features of the invention should become apparent to those skilled in the art from the following description of the preferred embodiments taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention, the invention not being limited to any particular preferred embodiment(s) disclosed. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0018]    These, as well as other features, aspects, and advantages of this invention, will be more completely understood and appreciated by referring to the following more detailed description of the presently preferred exemplary embodiments of the invention in conjunction with the accompanying drawings, of which: 
           [0019]      FIG. 1  is a sectional view of a film prepared in accordance with an exemplary embodiment of the present invention. 
           [0020]      FIG. 2  is a flow diagram of a method of making a film in accordance with the present invention. 
       
    
    
       [0021]    Unless otherwise indicated, the illustrations in the above figures are not necessarily drawn to scale. 
       DETAILED DESCRIPTION OF THE INVENTION 
       [0022]    The present invention is now illustrated in greater detail by way of the following detailed description that represents the best presently known mode of carrying out the invention. However, it should be understood that this description is not to be used to limit the present invention, but rather, is provided for the purpose of illustrating the general features of the invention. 
         [0023]    The invention relates to composition and manufacture of polyvinyl chloride (“PVC”) replacement films. The films of the present invention do not contain PVC and hence are called non-PVC films. The non-PVC films offer the advantage of being environmentally friendly and having the property of conformability, durability, or printability of PVC films. The non-PVC films of the present invention have properties and performance that are comparable to, or exceed, those of the PVC films, and are suitable for applications where PVC films are generally used, including for example, signs, graphics, wall covering, pressure sensitive products and the like. 
         [0024]      FIG. 1  is a sectional view of an exemplary film prepared in accordance with the present invention. The film is generally depicted by reference to numeral  5  and includes a release liner  10 , such as a silicone coated material, a pressure sensitive adhesive layer  20 , a strengthening layer  30 , and a print layer  40 . 
         [0025]    The adhesive layer  20  generally can be classified into the following categories: random copolymer adhesives such as those based upon acrylate and/or methacrylate copolymers, α-olefin copolymers, silicone copolymers, chloroprene/acrylonitrile copolymers, and the like; and block copolymer adhesives including those based upon linear block copolymers (i.e., A-B and A-B-A type), branched block copolymers, star block copolymers, grafted or radial block copolymers, and the like, and natural and synthetic rubber adhesives. 
         [0026]    A description of useful pressure-sensitive adhesives can be found in Encyclopedia of Polymer Science and Engineering, Vol. 13. Wiley-Interscience Publishers (New York, 1988). Additional descriptions of useful pressure-sensitive adhesives can be found in Encyclopedia of Polymer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964). 
         [0027]    The liner  10  is preferably an ultrathin or ultra light liner having a thickness of less than 1.02 mil (0.0255 mm), less than 1 mil (0.0254 mm), less than 0.8 mil (0.0203 mm), less than 0.6 mil (0.015 mm), less than 0.50 mil (0.013 mm), or equal to or less than 0.25 mil (0.00626 mm). Such thin liners are commercially available as HOSTAPHAN® polyester film (e.g., 0.5 mil, 0.0127 mm, Tradename 2SLK silicone coated film) sheeting from Mitsubishi Chemical Company of Tokyo Japan. Another liner material is provided by Avery Dennison Corporation of Pasadena, Calif. as a 1.02 mil (0.026 mm) polyester backing sheet with a 1.25 mil (0.032 mm) adhesive layer. 
         [0028]    The strengthening layer  30  can include a blend of cross linkable vinyl acetate copolymer and VAE emulsions, or it can be a polyurethane containing emulsions. The print layer  40  can include in exemplary embodiments a vinyl acetate containing polymer, a blend of vinyl acetate with VAE, a VAE/acrylic hybrid, an all acrylic formulation, or a VAE emulsion. 
         [0029]    The exemplary embodiments of composition and film  5  of the present invention include at least one of the following:
       (1) Vinyl acetate ethylene (“VAE”),   (2) VAE-acrylic hybrid   (3) Vinyl acetate homopolymer,   (4) Blend of VAE and vinyl acetate homopolymer,   (5) Blend of VAE and vinyl acetate copolymer,   (6) Blend of VAE with polyurethane,   (7) Blend of VAE with acrylic copolymer,   (8) Cross linking of VAE by adding small content of silane,   (9) Acrylic copolymer   (10) Polyurethane containing polymer, and/or   (11) Blend of Polyurethane and acrylic       
 
         [0041]    In other embodiments, a pigment, e.g., Titanium dioxide (“TiO 2 ”) and/or other pigments, can be added to any of the above ten embodiments of composition and film of the present invention. The opacity of the film  5  depends on the amount of TiO 2  or other materials. In another embodiment, the pigment, e.g., TiO 2 , can be replaced with latex such as ROPAQUE OP-96 or ULTRA-OPAQUE, made by Rohm and Haas of Philadelphia, Pa. In another embodiment, pigment like TiO 2  may not be included if a clear film is desired. In a further embodiment, CYMEL 385 by Cytec Industries Inc. of West Paterson, N.J. can be used as a cross-linker to increase the tensile strength of the film. In another embodiment used for nonprinting applications, wax emulsion, e.g., MICHEM GUARD 55 from Michelman of Cincinnati, Ohio, can be added to any of the above ten embodiments of composition and film, thereby providing the property of ease-of-cleaning to the film. In yet another embodiment, wax emulsion, e.g., MICHEM EMULSION 47950 from Michelman can be added to any of the above ten embodiments of composition and film of the present invention, and the manufactured film can be useful for anti-graffiti applications. The present invention further includes a method of making the film. 
         [0042]    In other embodiments, the carboxyl containing components of the print layer are crosslinkable using polyaziridine, for example, XAMA-7 from Lubrizol. The hydroxy containing components are crosslinkable using polyaziridine or melamine formaldehyde, e.g. CYMEL 385 from Cytec Industries Inc. Other crosslinkers known to the skilled in the art can also be used to cross link the print layer components. 
         [0043]    The film  5  of the present invention can be formed by preparing a liquid formulation or emulsion of an embodiment of composition of the present invention and then coating, such as by curtain coating, a substrate with the formulation or emulsion. In one embodiment, the substrate is a liner. In another embodiment, the substrate is a polyethylene terephthalate (“PET”) film. 
         [0044]    An exemplary method of making a film according to the present invention is illustrated in the flowchart  50  of  FIG. 2 . After starting at step  60 , the next step  70  is to provide components and a substrate. Next, at step  80 , the components are blended to form a composition. The composition includes a vinyl acetate containing polymer and at least one additive. Next, at step  90 , the substrate is coated with the composition. At step  100 , the composition is dried, and then, at step  110 , the dried composition is removed from the substrate. The method ends at step  120 . 
         [0045]    In another embodiment of the film  5  of the invention, a blend of polyvinyl acetate (“PVA”) and surfactant protected latex can be used to provide gloss higher than 60%. In a further embodiment, small-size latex can be used to provide higher gloss (about 75%). In another embodiment, matte or glossy film can be made by coating and then laminating with a pressure sensitive adhesive (“PSA”). 
         [0046]    In an embodiment of the method of the present invention, a dual-layered film  5  including a layer of the composition of the present invention and a layer of PSA is made using a dual-layer die coating process described in U.S. Pat. No. 5,728,430 to Sartor et al. and U.S. Pat. No. 5,558,913, et al. both of which are incorporated herein by reference in their entireties. 
         [0047]    Adhesives can be applied to one or both major surfaces of the film  5  using known processes, such as, for example, adhesive lamination. Halogen free adhesives can be used to produce halogen-free films. Examples of halogen-free adhesives include acrylic adhesives such as a hot-melt acrylic adhesive and a water-based latex acrylic adhesive. Other halogen-free adhesives include a hot-melt rubber adhesive, a silicone adhesive, thermoplastic elastomers, other halogen-free adhesives known in the art, and any combination of any of these in any proportion. 
         [0048]    In an exemplary embodiment of the composition of present invention, the polymeric material includes vinyl acetate containing polymer with a vinyl acetate content of at least about 75%, a pigment, and a dispersant. In yet another exemplary embodiment of the composition, the polymeric material includes a vinyl acetate containing polymer with a vinyl acetate content of at least 75%, a pigment, a plasticizer, a dispersant, a wetting agent, and an ultra-violet light (“UV”) stabilizer. In other embodiments of the composition, a binder with high glass-transition temperature (“Tg”) e.g., VINAC XX-230 or VINAC 890DNP by Air Products LP of Allentown, Pa., is added in varying quantities to manipulate the mechanical properties of the film  5  formed using the composition. Generally, for a polymer, higher Tg relates to higher tensile strength and lower % elongation. The mechanical properties can also be manipulated by adding plasticizer. The film of the present invention can be abrasion resistant, easy to cut, and in some cases biodegradable. 
         [0049]    Test Methods 
         [0050]    The properties of the composition and film  5  of the present invention can be characterized by various analytical techniques. A brief description of these analytical techniques is given below: 
         [0051]    Tensile Elongation 
         [0052]    The tensile elongation of the film  5  is tested using mechanical properties measurement techniques, e.g., Instron. A modified ASTM D882 was used to determine the tensile strength and percentage elongation of the films of the present invention. The procedure is as follows:
       1. A 1″×4″ specimen was cut out in the machine direction.   2. Grip the film 1″ from the end at both the ends, so the separation between the grips is 2 inches.   3. Set the crosshead speed at 12 inches per minute (“ipm”).   4. Obtain the tensile strength, which is the product of tensile stress times the thickness of the film.   5. The % elongation is reported by the machine.       
 
         [0058]    The standard requires a minimum ultimate elongation of 50% and a minimum tensile strength of 0.5 pound per square inch (“psi”). The presence or absence of PSA on the film does not appreciably alter the strength and/or elongation of the film. As such, wherever the film in the examples below includes PSA, the tensile elongation test was performed using film without the layer of PSA. 
         [0059]    Printability 
         [0060]    The printability of the film  5  is tested by printing directly on the film specimen using solvent-based ink-jet printer. Other printing methods can include, for example, solvent screen, eco-solvent, digital, piezo ink-jet, UV screen, and UV ink-jet processes. Next, visual inspection is performed to determine if there was smudging of ink on the surface of the film and diffusion of ink inside the film. Good printing is obtained if there is no smudging and diffusion of ink. 
         [0061]    Durability 
         [0062]    The durability of the film  5  is tested using xenon arc weather-o-meter according to the standards of SAE J1960 (Rev. October 2004). The test method is designed to accelerate extreme environmental conditions such as sunlight, heat, and moisture (in the form of humidity, condensation, or rain) for the purpose of predicting the weatherability of the films. 
       EXAMPLES 
       [0063]    The following examples describe the various embodiments of the present invention. Numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art and the present invention is not limited to the examples given below. Unless otherwise states, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained, or are available, from the chemical supplier identified below, or can be synthesized by conventional techniques. 
         [0064]    The following Table 1 provides a list of chemicals used in the following examples, identifying their supplier; function; chemical name, formula or type; percentage solids; and Tg. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Materials Used in Examples 
               
             
          
           
               
                   
                   
                   
                   
                 % 
                   
               
               
                 Material Description 
                 Supplier 
                 Function 
                 Chemical 
                 Solids 
                 Tg ° C. 
               
               
                   
               
             
          
           
               
                 KRONOS 4311 
                 Kronos 
                 Pigment 
                 TiO2 
                 77 
                   
               
               
                 ZONYL FS-300 
                 Du Pont 
                 Surfactant 
                 Flurosurfactant 
                 40 
               
               
                 TAMOL 731A 
                 Rohm Haas 
                 dispersant 
                 hydrophobic 
                 25 
               
               
                   
                   
                   
                 copolymer 
               
               
                 AIRFLEX 465 
                 Air Products 
                 Binder 
                 VAE Emulsion 
                 67 
                 −5 
               
               
                 VINAC XX-230 
                 Air Products 
                 Binder 
                 VA Emulsion 
                 55 
                 30 
               
               
                 AIRFLEX 323 
                 Air Products 
                 Binder 
                 VAE Emulsion 
                 55 
                 22 
               
               
                 VINAC 890DPN 
                 Air Products 
                 Binder 
                 VA copolymer 
                 49 
                 30 
               
               
                 HYCAR 26349 
                 Lubrizol 
                 Binder 
                 Acrylic Latex 
                 49 
                 12 
               
               
                 HYCAR 26348 
                 Lubrizol 
                 Binder 
                 Acrylic Latex 
                 48.5 
                 30 
               
               
                 JONCRYL 617A 
                 Johnson 
                 Binder 
                 Acrylic Latex 
                 45.5 
                 7 
               
               
                   
                 Polymer 
               
               
                 SANCURE 899 
                 Lubrizol 
                 Binder 
                 PU Emulsion 
                 35 
               
               
                 BENZOFLEX 2088 
                 Velsicol 
                 Plasticizer 
                 Dipropylene 
               
               
                   
                 Chemical 
                   
                 Glycol 
               
               
                   
                   
                   
                 dibenzoate 
               
               
                 DREWPLUS L-198 
                 Ashland Inc. 
                 Defoamer 
                 Aliphatic 
               
               
                   
                   
                   
                 Petroleum 
               
               
                 DYNASYLAN GLYEO 
                 Degussa 
                 coupling agent 
                 Silane 
               
               
                 DYNASYLAN 
                 Degussa 
                 coupling agent 
                 Silane 
               
               
                 HYDROSIL 2926 
               
               
                 Butyl cellusolve 
                 Dow Chemical 
                 solvent 
               
               
                 TINUVIN 1130 
                 Ciba 
                 UV absorber 
                 hydroxyphenyl 
               
               
                   
                   
                   
                 benzotriazole 
               
               
                 TINUVIN 292 
                 Ciba 
                 light stabilizer 
                 sebacate type 
               
               
                 CYMEL 385 
                 Cytec Industries 
                 Crosslinker 
                 Melamine 
               
               
                   
                 Inc. 
                   
                 formaldehyde 
               
               
                 EVOCAR LATEX DA- 
                 Dow Chemical 
                 Binder 
                 VAE 
                 55 
                 12 
               
               
                 280 
               
               
                 TRITON X-405 
                 Dow Chemical 
                 Surfactant 
                 Octylphenol 
                 70 
               
               
                   
                   
                   
                 ethoxylate 
               
               
                 TRITON X-45 
                 Dow Chemical 
                 Surfactant 
                 Octylphenol 
                 100 
               
               
                   
                   
                   
                 ethoxylate 
               
               
                 XAMA 7 
                 Lubrizol 
                 Crosslinker 
                 Polyaziridine 
                 95 
               
               
                 HYCAR 26-1265 
                 Lubrizol 
                 Binder 
                 Acrylics 
                 49 
                 23 
               
               
                   
                   
                   
                 Ethoxylated 
               
               
                   
                   
                   
                 polyol 
               
               
                 DISPONIL AFX4030 
                 Cognis 
                 Surfactant 
                 Blend 
                 30 
               
               
                 RHEOLATE 350 
                 Elementis 
                 Thickener 
                 Polyurethane 
                 50 
               
               
                 DEV 5147 
                 Avery Dennison 
                 Binder 
                 VAE/acrylics 
                 60 
                 12-40 
               
               
                   
               
             
          
         
       
     
         [0065]    The chemicals used in the examples are further described below. 
         [0066]    AIRFLEX 465: A low viscosity/high solids (67%), polyvinyl alcohol protected Vinyl Acetate-ethylene (“VAE”) emulsion with rapid set speed, available from Air Products. 
         [0067]    AIRFLEX 323: Polyvinyl alcohol protected VAE emulsion, with standard solids (55%), high Tg, and excellent heat resistance, available from Air Products. 
         [0068]    DISPONIL AFX 4030: Nonionic surfactant at with 40 moles ethylene oxide at 30% solids, available from Cognis Corporation of Cincinnati, Ohio. 
         [0069]    VINAC XX-230: Polyvinyl alcohol protected VA emulsion, with standard solids at 55%, available from Air Products. 
         [0070]    VINAC 890DPN: Polyvinyl acetate dispersion containing reactive groups, aluminum chloride hardener and small parts of a coalescence agent. Solids content is 49%, available from Air Products. 
         [0071]    TAMOL 731A: A hydrophobic copolymer dispersant with excellent compatibility and good pigment wetting, available from Rohm Haas. 
         [0072]    HYCAR 26349: Surfactant protected acrylic latex at 49% solids and 12° C. Tg, for durable coating/adhesives, available from The Lubrizol Corporation of Wickliffe, Ohio. 
         [0073]    HYCAR 26348: Surfactant protected acrylic latex at 48.5% solids and 30° C. Tg, excellent oil and solvent resistance, available from The Lubrizol Corporation. 
         [0074]    HYCAR 26-1265: Surfactant protected acrylic latex at 49% solids and 23° C. Tg, for ultra water resistance coating/adhesives, available from The Lubrizol Corporation. 
         [0075]    RHEOLATE 350: A rheological additive from Elementis of London, United Kingdom. 
         [0076]    DEV 5147: VAE/acrylic hybrid; Scale-up version of 1277-72. 
         [0077]    SANCURE 899: An aliphatic polyester polyurethane dispersion at 30% solids, provides high gloss for coatings, available from The Lubrizol Corporation. 
         [0078]    ZONYL FS-300: A general purpose nonionic fluorosurfactant that is an ideal wetting and leveling agent for aqueous application at 40% solids, available from DuPont of Wilmington, Del. 
         [0079]    BENZOFLEX 2088: A dipropylene glycol dibenzoate plasticizer, available from Velsicol Chemical Corporation of Rosemont, Ill. 
         [0080]    KRONOS 4311: An aqueous dispersion of titanium dioxide at 77% solids, available from Kronos of Houston, Tex. 
         [0081]    JONCRYL 617A: Acrylic latex at 45.5% solids, 7° C. Tg, available from Johnson Polymer of Racine, Wis. 
         [0082]    DREWPLUS L-198: An aliphatic petroleum defoamer, available from Ashland Inc. of Columbus, Ohio. 
         [0083]    Butyl Cellusolve: An ethylene glycol butyl ether solvent, available from Dow Chemical of Midland, Mich. 
         [0084]    CYMEL 385: A melamine formaldehyde cross linking agent, available from Cytec Industries Inc. 
         [0085]    TINUVIN 1130: A UV absorber of the hydroxyphenyl benzotriazole class, available from Ciba of Basel, Switzerland. 
         [0086]    TINUVIN 292: A liquid hindered amine light stabilizer for coating applications, available from Ciba. 
         [0087]    DYNASYLAN GLYEO: A silane coupling agent (3-glycidyloxy-propyl-triethoxy silane), available from Degussa of Parsippany, N.J. 
         [0088]    DYNASYLAN HYDROSOL 2926: A silane coupling agent (3-glycidyloxy-propyl-trialkoxy silane), available from Degussa. 
         [0089]    EVOCAR LATEX DA-280: VAE latex, available from Dow Chemical. 
         [0090]    TRITON X-405: Nonionic surfactant, available from Dow Chemical. 
         [0091]    TRITON X-45: Nonionic surfactant, available from Dow Chemical. 
         [0092]    XAMA 7: Polyaziridine, available from The Lubrizol Corporation. 
         [0093]    1277-5A: Latex prepared according to Example 27A. 
         [0094]    1277-5A: Latex prepared according to Example 27A. 
         [0095]    1277-70: Latex prepared according to Example 28A. 
         [0096]    1277-72A: Latex prepared according to Example 28A. 
         [0097]    DEV-5147: Latex prepared according to Example 28A, available from Avery Dennison Corporation. 
       Example 1 
       [0098]    In separate containers, the following mixtures were prepared:
       A. 32.5 parts of KRONOS 4311 (25 parts dry)   B. 2.5 part of water and 0.26 part of ZONYL FS-300   C. 2.5 parts TAMOL 731A (0.6 part dry)   D. 181 parts of AIRFLEX 323 (100 parts dry)   E. 0.2 part of DREWPLUS L-198       
 
         [0104]    Components A, B, and C were mixed well and added to D, and then, E was added. The blend was then coated over a 1.4 mil PET film. The resulting VAE film was then peeled off from the PET film. 
       Example 2 
       [0105]    In separate containers, the following mixtures were prepared:
       A. 30.8 parts of AIRFLEX 465 (20 parts dry) and 145 parts of AIRFLEX 323 (80 parts dry)   B. 2.5 part of water and 0.26 part of ZONYL FS-300   C. 19.5 parts of KRONOS 4311   D. 0.2 part of DREWPLUS L-198       
 
         [0110]    Component B was mixed well and added to C, and then, the mixture was added to A under agitation, and next D was added. The resulting solids were 58%. The blend was then coated over a 2 mil PET film. The resulting VAE film was then peeled off from the PET film. 
         [0111]    The above formulation of Example 2 was then prepared in a larger amount. The blend was coated on 2 mil PET at a 2.7 mil thickness. The coated film was then printed using a MIMAKI JV3 solvent ink jet printer available from Mimaki Engineering Co., Ltd. of Nagano, Japan. No color-to-color bleed was observed by visual inspection, and the quality of print was good. 
       Example 3 
       [0112]    The composition of the formulation was the same as in Example 2. The formulation was scaled-up to a large volume and then coated in a pilot coater over 1.4 mil PET. The coated film was then laminated to a PSA with release liner. The coated film was about 1.9 mil. In other embodiments, the formulation is coated in the pilot coater over 0.92 mil PET or 2.0 mils PET. After peeling off the PET film, the gloss level was 82 and 96 at a 60 and 85 degree angle, respectively. 
         [0113]    The same formulation was then coated using a dual die method over a release liner with VAE emulsion on the top and PSA emulsion (AROSET 3300 from Ashland Inc.) in between the VAE emulsion and the release liner. In addition to coating using a dual die method, in other embodiments, the formulation is coated using slide coating, reverse scroll, slot die, and/or curtain coating methods. In wet state, it formed a good two-layer type of coating. 
       Example 4 
       [0114]    The composition of the formulation was the same as in A of Example 2, except the binder system was 30 parts dry AIRFLEX 465 and 70 parts dry AIRFLEX 323. 
       Example 5 
       [0115]    The composition of the formulation was the same as in A of Example 2, except the binder system was 43 parts dry VINAC 230 and 57 parts dry AIRFLEX 323 at 20 parts BENZOFLEX 2088. 
       Example 6 
       [0116]    The composition of the formulation was the same as Example 5 except VINAC 890DPN was used instead of VINAC XX-230. Also, 21 parts of BENZOFLEX 2088 were used instead of 20 parts. 
       Example 7 
       [0117]    The same as Example 6 except no BENZOFLEX 2088 was used in the formulation. 
       Example 8 
       [0118]    The same as Example 6 except 5 parts of BENZOFLEX 2088 were used. 
       Example 9 
       [0119]    The same as Example 6 except 10 parts of BENZOFLEX 2088 were used. 
       Example 10 
       [0120]    The same as Example 5 except 10 parts of BENZOFLEX 2088 were used. 
       Example 11 
       [0121]    The same as Example 2 except 0.4 part of TAMOL 731A was included in the formulation. Also, 18 parts of KRONOS 4311 were used instead of 15 parts. 
       Example 12 
       [0122]    The same as Example 11 except 25 parts of KRONOS 4311 were used instead of 18 parts. 
       Example 13 
       [0123]    The same as Example 5 except 70 parts of AIRFLEX 323 and 30 parts of VINAC XX-230 were used instead of 57 parts of AIRFLEX 323 and 43 parts of VINAC XX-230. Also, the amount of BENZOFLEX 2088 was 5 parts instead of 20 parts. 
       Example 14 
       [0124]    The same as Example 1 except 90 parts of AIRFLEX 323 and 10 parts of VINAC XX-230 were used instead of 100 parts AIRFLEX 323, respectively. Also, 0.4 part of TAMOL 731A was used instead of 0.6 part. 
       Example 15 
       [0125]    The same as Example 14, except 80 parts of AIRFLEX 323 and 20 parts of VINAC XX-230 were used instead of 90 parts of AIRFLEX 323 and 10 parts of VINAC XX-230, respectively. 
       Example 16 
       [0126]    The same as Example 14 except 10 parts of VINAC XX-230 were replaced by 10 parts VINAC 890DPN. 
       Example 17 
       [0127]    The same as Example 15 except 20 parts of VINAC XX-230 were replaced by 20 parts of VINAC 890DPN. 
       Example 18 
       [0128]    The same as Example 15 except 20 parts of VINAC XX-230 were replaced by 20 parts of HYCAR 26349. 
       Example 19 
       [0129]    The same as Example 15 except 20 parts of VINAC XX-230 were replaced by 20 parts of HYCAR 26348. 
       Example 20 
       [0130]    The same as Example 15 except 20 parts of VINAC XX-230 were replaced by 20 parts of JONCRYL 617A. 
       Example 21 
       [0131]    The same as Example 15 except 20 parts of VINAC XX-230 were replaced by 20 parts of SANCURE 899. 
       Example 22 
       [0132]    The same as Example 1 except 2 parts of DYNASYLAN GLYEO also were included in the formulation. 
       Example 23 
       [0133]    The same as Example 1 except 2 parts of DYNASYLAN HYDROSIL 2926 also were included in the formulation. 
       Example 24 
       [0134]    The composition of the formulation was the same as Example 4 except 2 parts of TINUVIN 1130 and 1 part of TINUVIN 292 were dissolved in 5 parts of ethylene glycol n-butyl ether (Aldrich) and added to the blend. The coated film  5  was tested using a xenon weather-o-meter for durability. 
         [0135]    The compositions of the various formulations used in the above examples are summarized in Table 2 below. Table 3 summarizes film thickness, opacity, and mechanical properties of the coated films. 
       Example 25 
       [0136]    The same as Example 15 except 80 parts of AIRFLEX 323 and 20 parts of VINAC XX-230 were replaced by 50 parts of HYCAR 26349 and 50 parts of HYCAR 26348, respectively. 
       Example 26 
       [0137]    The same as Example 15, except 3 parts of CYMEL 385 were included in the formulation. 
       Example 27A 
     VAE-Acrylic Hybrid Emulsion Preparation 
       [0138]    Following solutions are prepared:
       A1: 273 gm of EVOCAR LATEX DA-280   A2: 1 gm water and 1 gm of TRITON X-405   A3: 2 gm of butyl acrylate and 6 gm of methyl methacrylate   B1: 30 gm of water, 12 gm TRITON X-405, and 0.9 gm TRITON X-45   B2: 50 gm of butyl acrylate, 100 gm methyl methacrylate, and 7.5 gm acrylic acid   C: 18 gm water and 0.6 gm of t-butyl hydrogen peroxide   D: 18 gm water, 0.6 gm sodium formaldehyde sulfoxylate, 0.1 gm TRITON X-405.       
 
         [0146]    Process:
       1. A1 and A2 were charged to the 1-Liter reactor and purge with nitrogen for at least 30 minutes.   2. Start agitation and add A3.   3. Make a pre-emulsion of B by adding B2 to B1 under high-shear mixing.   4. Start heating up, and at 50° C., start adding slowly C and D over 3 hours.   5. 10 minutes later, start adding slowly B over 2 hours at 55° C.   6. After the slow-adds, continue slow-adding C and D for another 30 minutes. Then cool and discharge.       
 
         [0153]    The resulting latex (1277-5A) has 4.5 pH, 70 centipoise (“cps”) in viscosity at 62.3% solids. 
       Example 27B 
       [0154]    The formulation is the same as Example 15, except that latex 1277-5A is prepared according to Example 27A was adjusted to pH 7 by adding 7% ammonium hydroxide solution and was then used instead of AIRFLEX 323 and VINAC XX-230. Also, TAMOL 731A was not used. 
       Example 27C 
       [0155]    The same as 27B except 2% XAMA 7 (polyaziridine) was included. 
       Example 28A 
       [0156]    Following latexes were made with the process as Example 27. The main composition is listed below. 
         [0000]    
       
         
               
               
             
               
               
               
               
             
               
               
             
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Code 
               
             
          
           
               
                   
                 1277-70 
                 1277-72 
                 DEV 5147 
               
             
          
           
               
                   
                 Scale 
               
             
          
           
               
                   
                 1L 
                 1L 
                 Drum 
               
               
                   
                   
               
             
          
           
               
                 Composition 
               
             
          
           
               
                   
                 EVOCA DA280* 
                 100 
                 100 
                 100 
               
               
                   
                 BA 
                 56 
                 30 
                 30 
               
               
                   
                 MMA 
                 111 
                 70 
                 70 
               
               
                   
                 AA 
                 8.3 
                 5 
                 5 
               
             
          
           
               
                 Physical Properties 
               
             
          
           
               
                   
                 % Solids 
                 63.6 
                 62 
                 60.8 
               
               
                   
                 pH 
                 6.9 
                 7.0 
                 7.5 
               
               
                   
                 Viscosity (cps) 
                 220 
                 42 
                 1020 
               
               
                   
                   
               
               
                   
                 *Dry 
               
             
          
         
       
     
       Example 28B 
       [0157]    In separate containers, the following mixtures were prepared:
       F. 157.2 parts of 1277-70 (100 parts dry)   G. 1.5 parts of water and 1.5 parts of TRITON X-405   H. 2 part of water and 0.23 part of ZONYL FS-300   I. 1.6 parts TAMOL 731A (0.4 part dry)   J. 32.5 parts of KRONOS 4311 (25 parts dry)   K. 0.2 part of DREWPLUS L-198   L. 1 part of water and 1 part of XAMA 7       
 
         [0165]    The components were added to a glass container under mixing. The blend was then coated over a 1.42 mil PET film at 2-mil thick. 
       Example 28C 
       [0166]    The same as 28B except 2 parts of water and 2 parts of XAMA 7 were used in G. 
       Example 28D 
       [0167]    The same as 28B except 163.4 gm of 1277-72 latex were used in A. 
       Example 28E 
       [0168]    The same as 28D except 2 parts of water and 2 parts of XAMA-7 were used in G. 
         [0169]    Printing quality of the above 4 coated films 5 (Examples 28B, C, D, E) were quite similar to the cast vinyl by a digital ink jet printer. 
       Example 29A 
       [0170]    The same as Example 28B, Except 164 gm of DEV 5147 were used in A, 2.3 gm of DISPONIL AFX 4030 were used in B, and no XAMA-7 was used in G. The resulting formulation was coated over 1.42 mil PET at 1.8 mil (refer as print layer). On the top of this coated film, it was further coated with the following emulsion blends strengthening layer: 52 parts of VINAC DPN 890, 45 parts of DUR-O-SET E130, 1 part of water, and 0.3 part of ZONYL FS300 at different thickness. The coated film was dried in the 85° C. oven for 5 minutes. 
       Example 29B 
       [0171]    The same as Example 29A except HYCAR 26-1265 was used instead of DEV 5147 in A and 1 part of water and 1 part of XAMA-7 were used in G. For coating purpose, 1.3 parts of RHEOLATE 350 were added to increase the coating viscosity. The resulting coating has 1.5 mils in thickness. On the top of this film, it was also coated at different thickness. The following table shows the performance. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Thickness 
                 Mechanical Properties 
                   
               
             
          
           
               
                   
                 (mil) 
                 Tensile (lb/in) 
                 % 
                 Young&#39;s 
                   
               
             
          
           
               
                   
                 Print 
                   
                 at 
                   
                 Elongation 
                 Modulus 
                 Opacity 
                   
                 Digital 
               
               
                 Example 
                 layer 
                 S.L.* 
                 yield 
                 at break 
                 at break 
                 (Mpa) 
                 (%) 
                 Weeding 
                 Printing 
               
               
                   
               
             
          
           
               
                 29A 
                 1.8 
                 0.0 
                 2.7 
                 2.6 
                 127 
                 389 
                 91.95 
                 poor 
                   
               
               
                   
                 1.8 
                 0.5 
                 4.6 
                 4.8 
                 199 
                 494 
                 90.61 
                 poor 
               
               
                   
                 1.8 
                 1.5 
                 4.6 
                 4.8 
                 199 
                 494 
                 90.61 
                 marginal 
                 good 
               
               
                   
                 1.8 
                 1.8 
                 7.7 
                 8.8 
                 256 
                 670 
                 90.90 
                 good 
               
               
                 29B 
                 1.5 
                 0.0 
                 0.9 
                 3.0 
                 282 
                 273 
                 90.65 
                 poor 
               
               
                   
                 1.5 
                 0.7 
                 2.6 
                 5.4 
                 340 
                 357 
                 91.09 
                 marginal 
               
               
                   
                 1.5 
                 1.0 
                 3.5 
                 5.2 
                 260 
                 417 
                 91.45 
                 v.good 
                 good 
               
               
                   
                 1.5 
                 1.4 
                 4.4 
                 7.8 
                 365 
                 466 
                 91.42 
                 good 
               
               
                   
               
               
                 *strengthening layer 
               
             
          
         
       
     
         [0172]    The results suggest that both VAE/acrylic hybrid and acrylic base films  5  can be made at high tensile with strengthening layer. The laminate was made by laminating with PSA transfer tape with liner to the strengthening layer, and removal of the PET. The resulting laminate can be printed and weeded well. 
       Example 30 
       [0173]    Examples of 30A and 30B are same composition as 29A and 29B with different thickness of the strengthening layer respectively. The results are in the Table below. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                   
                   
                 Gloss 
               
               
                   
                 Thickness (mil) 
                 Tensile (lb/in) 
                 % Elongation 
                   
                 60 
               
             
          
           
               
                 Sample ID 
                 print 
                 S.L. 
                 total 
                 at yield 
                 at break 
                 at break 
                 Opacity 
                 Degree 
               
               
                   
               
               
                 30A 
                 2.0 
                 1.7 
                 3.7 
                 7.1 
                 8.5 
                 180 
                 91.1 
                 84.0 
               
               
                 30B 
                 2.0 
                 1.3 
                 3.3 
                 5.2 
                 8.2 
                 230 
                 91.5 
                 91.4 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 Composition of formulations used in Examples 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 AIRFLEX 
                 HYCAR 
                 VAE/ 
                 AIRFLEX 
                 VINAC 
                 VINAC 
                 HYCAR 
                 HYCAR 
                 JONCRYL 
               
               
                 Example 
                 323 
                 26-1265 
                 acrylic 
                 465 
                 230 
                 890DPN 
                 26348 
                 26349 
                 617A 
               
               
                   
               
               
                  1 
                 100 
               
               
                  2 
                 80 
                   
                   
                 20 
               
               
                  3 
                 80 
                   
                   
                 20 
               
               
                  4 
                 70 
                   
                   
                 30 
               
               
                  5 
                 57 
                   
                   
                   
                 43 
               
               
                  6 
                 57 
                   
                   
                   
                   
                 43 
               
               
                  7 
                 57 
                   
                   
                   
                   
                 43 
               
               
                  8 
                 57 
                   
                   
                   
                   
                 43 
               
               
                  9 
                 57 
                   
                   
                   
                   
                 43 
               
               
                 10 
                 57 
                   
                   
                   
                 43 
               
               
                 11 
                 80 
                   
                   
                 20 
               
               
                 12 
                 80 
                   
                   
                 20 
               
               
                 13 
                 70 
                   
                   
                   
                 30 
               
               
                 14 
                 90 
                   
                   
                   
                 10 
               
               
                 15 
                 80 
                   
                   
                   
                 20 
               
               
                 16 
                 90 
                   
                   
                   
                   
                 10 
               
               
                 17 
                 80 
                   
                   
                   
                   
                 20 
               
               
                 18 
                 80 
               
               
                 19 
                 80 
                   
                   
                   
                   
                   
                 20 
               
               
                 20 
                 80 
                   
                   
                   
                   
                   
                   
                   
                 20 
               
               
                 21 
                 80 
               
               
                 22 
                 100 
               
               
                 23 
                 100 
               
               
                 24 
                 70 
                   
                   
                 30 
               
               
                 25 
                   
                   
                   
                   
                   
                   
                 50 
                 50 
               
               
                 26 
                 80 
                   
                   
                   
                 20 
               
               
                 27B 
                   
                   
                 100 
               
               
                 27C 
                   
                   
                 100 
               
               
                 28B 
                   
                   
                 100 
               
               
                 28C 
                   
                   
                 100 
               
               
                 28D 
                   
                   
                 100 
               
               
                 28E 
                   
                   
                 100 
               
               
                 29A 
                   
                   
                 100 
               
               
                 29B 
                   
                 100 
                   
               
               
                 30A 
                   
                   
                 100 
               
               
                 30B 
                   
                 100 
               
               
                   
               
             
          
           
               
                   
                   
                 XAMA 
                 CYMEL 
                 KRONOS 
                 TAMOL 
                 BENZOFLEX 
                 TINUVIN 
                 Tinuvin 
               
               
                   
                 Example 
                 7 
                 385 
                 4311 
                 731A 
                 2088 
                 1130 
                 292 
               
               
                   
                   
               
               
                   
                  1 
                   
                   
                 20 
                 0.6 
               
               
                   
                  2 
                   
                   
                 15 
               
               
                   
                  3 
                   
                   
                 15 
               
               
                   
                  4 
                   
                   
                 15 
               
               
                   
                  5 
                   
                   
                 15 
                   
                 20 
               
               
                   
                  6 
                   
                   
                 15 
                   
                 21 
               
               
                   
                  7 
                   
                   
                 15 
               
               
                   
                  8 
                   
                   
                 15 
                   
                 5 
               
               
                   
                  9 
                   
                   
                 15 
                   
                 10 
               
               
                   
                 10 
                   
                   
                 15 
                   
                 10 
               
               
                   
                 11 
                   
                   
                 18 
                 0.4 
               
               
                   
                 12 
                   
                   
                 25 
                 0.4 
               
               
                   
                 13 
                   
                   
                 15 
                   
                 5 
               
               
                   
                 14 
                   
                   
                 25 
                 0.4 
               
               
                   
                 15 
                   
                   
                 25 
                 0.4 
               
               
                   
                 16 
                   
                   
                 25 
                 0.4 
               
               
                   
                 17 
                   
                   
                 25 
                 0.4 
               
               
                   
                 18 
                   
                   
                 25 
                 0.4 
               
               
                   
                 19 
                   
                   
                 25 
                 0.4 
               
               
                   
                 20 
                   
                   
                 25 
                 0.4 
               
               
                   
                 21 
                   
                   
                 25 
                 0.4 
               
               
                   
                 22 
                   
                   
                 25 
                 0.6 
               
               
                   
                 23 
                   
                   
                 25 
                 0.6 
               
               
                   
                 24 
                   
                   
                 15 
                   
                   
                 2 
                 1 
               
               
                   
                 25 
                   
                   
                 25 
                 0.4 
               
               
                   
                 26 
                   
                 3 
                 25 
                 0.4 
               
               
                   
                 27B 
               
               
                   
                 27C 
                 2 
               
               
                   
                 28B 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                 28C 
                 2 
                   
                 25 
                 0.4 
               
               
                   
                 28D 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                 28E 
                 2 
                   
                 25 
                 0.4 
               
               
                   
                 29A 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                 29B 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                 30A 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                 30B 
                 1 
                   
                 25 
                 0.4 
               
               
                   
                   
               
               
                   
                 Note: 
               
               
                   
                 1. Compositions are normalized based on 100 dry binder. 
               
               
                   
                 2. All formulations contain about 0.26% ZONYL FS-300 and 0.2% DREWPLUS L-198 based on 100 parts dry binder 
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Properties of films made in Examples 
               
             
          
           
               
                   
                 Coated 
                   
                 Tensile 
                 % Elongation 
               
             
          
           
               
                   
                 Thickness 
                 % 
                 (lb/in) 
                 at 
                 at 
               
               
                 Example 
                 (mil) 
                 Opacity 
                 at Yield 
                 Yield 
                 Break 
               
               
                   
               
             
          
           
               
                  1 
                 2.5 
                 94 
                 1.7 
                 22 
                 260 
               
               
                  2 
                 2.8 
                 92 
                 1.7 
                 25 
                 310 
               
               
                  3 
                 1.9 
                 85 
                 0.9 
                 25 
                 380 
               
               
                  4 
                 2 
                 87 
                 0.7 
                 26 
                 280 
               
               
                  5 
                 2.75 
                 91 
                 0.5 
                 35 
                 300 
               
               
                  6 
                 2.7 
                 90 
                 0.4 
                 48 
                 366 
               
               
                  7 
                 3 
                 93 
                 5.3 
                 10 
                 237 
               
               
                  8 
                 2.8 
                 91 
                 2.9 
                 10 
                 357 
               
               
                  9 
                 3 
                 93 
                 2.1 
                 5 
                 390 
               
               
                 10 
                 3 
                 93 
                 1.3 
                 70 
                 375 
               
               
                 11 
                 2.4 
                 91 
                 1 
                 30 
                 250 
               
               
                 12 
                 2.3 
                 94 
                 1 
                 30 
                 291 
               
               
                 13 
                 2.6 
                 87 
                 2.1 
                 15 
                 312 
               
               
                 14 
                 2.3 
                 92 
                 1.8 
                 19 
                 279 
               
               
                 15 
                 2.4 
                 91 
                 2.2 
                 15 
                 237 
               
               
                 16 
                 2.2 
                 92 
                 1.5 
                 20 
                 348 
               
               
                 17 
                 2.2 
                 93 
                 2.1 
                 19 
                 191 
               
               
                 18 
                 2.1 
                 94 
                 1.3 
                 22 
                 273 
               
               
                 19 
                 2.4 
                 94 
                 2.1 
                 8 
                 140 
               
               
                 20 
                 2.3 
                 94 
                 1.2 
                 5 
                 250 
               
               
                 21 
                 2 
                 90 
                 0.6 
                 40 
                 249 
               
               
                 22 
                 2.3 
                 93 
                 0.7 
                 25 
                 395 
               
               
                 23 
                 2.3 
                 93 
                 1.4 
                 25 
                 313 
               
               
                 24 
                 2.5 
                 94 
                 0.4 
                 50 
                 365 
               
               
                 25 
                 2.1 
                 94 
                 4 
                 5 
                 65 
               
               
                 26 
                 2.3 
                 93 
                 3 
                 11 
                 210 
               
               
                 27B 
                 2.3 
                 96 
                 2.8 
                 8 
                 200 
               
               
                 27C 
                 2.5 
                 97 
                 3.6 
                 8 
                 150 
               
               
                   
               
             
          
         
       
     
         [0174]    All of the features disclosed in the specification, including the claims, abstract, and drawings, and all of the steps in any method or process disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. Each feature disclosed in the specification, including the claims, abstract, and drawings, can be replaced by alternative features serving the same, equivalent, or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features. 
         [0175]    Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.