Protective overlay film

Abstract: A protective overlay film comprising (1) a solvent-resistant, abrasion-resistant, and weather-resistant protective layer having an inner surface and an outer surface, and (2) an adhesive layer on the inner surface of the protective layer, wherein, the protective layer has a modulus at 2 percent elongation of at least 550 megaPascals, and is made from a mixture of at least one hydroxy-functional acrylic polyol and at least one polyfunctional curing agent. The acrylic polyol preferably has an effective T g of between about -20°C and about 30°C and preferably has an effective equivalent weight of between about 300 and about 6000. The curing agent typically comprises at least one polyfunctional isocyanate, aminoplast resin, azlactone, or combination thereof, and preferably has a functionality between about 2 and 20.

Description: Field of Invention The present invention relates to a protective overlay film which can be adhered to a desired substrate, e.g., the cover or top film of a retroreflective sheeting, to afford increased solvent-resistance, abrasion-resistance, and weather-resistance. Background Retroreflective sheetings are well known and have been widely used for safety and informational purposes, e.g., signs on vehicles or by roads or highways. In order to retain desired retroreflectivity even when wet, retroreflective sheetings typically comprise a cover film disposed in front of the microspheres. As disclosed in U.S. Patent 3,190,178 (McKenzie), such cover films can prevent water from collecting on the front surfaces of the microspheres such that the sheeting will remain retroreflective, even when wet. That patent discloses that such materials as methyl methacrylate, polyethylene terephthalate, cellulose acetate, or cellulose acetate butyrate may be used as cover film materials for such retroreflective sheeting which is sometimes referred to as "encapsulated-lens" sheeting. Other examples of cover film materials include polycarbonate, chlorosulfonated polyethylene, polystyrene, polypropylene, flexible epoxy resins, ethyl cellulose, and the like. In addition, "embedded-lens" retroreflective sheetings wherein the front surfaces of the microspheres are embedded in a top film are made with top films made from such materials as alkyd, acrylic, or plasticized polyvinyl chloride resins. As are other public signs, retroreflective signs are subject to unauthorized tampering, e.g., application of graffiti by spray paint or other means such as inks or waxes to the surfaces thereof, or attempts by vandals to damage or destroy the sign. Such signs are also subject to abrasive action or being soiled, e.g., by wind blown dirt. Many cover film materials used today, e.g, polymethyl methacrylate, polyvinyl chloride, and polycarbonate, tend to be difficult to clean or resist removal of paint therefrom. In many instances, paints, inks, waxes, or other graffiti materials may adhere tenaciously to the cover film so as to be difficult to remove. In some instances, even if the surface deposit of graffiti material, e.g, the layer of paint, can be removed, some of the components of the material will have penetrated into the cover film so as to remain visible, e.g., as a clouded region of reduced transmissivity or a colored region. Such regions may be merely aesthetically undesirable or may result in reduced retroreflective performance by the sign. Some cover film materials may tend to degrade when subject to environmental conditions, e.g., sunlight, high and low temperatures, humidity. For these reasons, in some instances a protective film may be provided over the cover film to protect same from degradation due to graffiti and environmental degradative effects. Many of the protective films in use today are formed from coatings applied in liquid form to the cover film of the retroreflective sheeting to be protected. Examples of such liquid coatings include acrylic urethane-based or acrylic melamine-based compositions. After application, the liquid composition is dried or cured, frequently resulting in evaporation of solvent, thereby forming the protective coating on the sheeting. Evaporation of solvents is typically undesirable and may be strictly regulated or even prohibited because of concerns regarding air and/or water pollution and toxicology. Furthermore, such application techniques may require use of special or expensive equipment such as sprayers or drying ovens and tend to be labor intensive, thereby entailing substantial cost. Moreover, the solvents used in such liquid may tend to attack the cover film, thereby impairing the performance thereof, or the resultant dried or cured coating may not attain sufficiently strong adhesion to the cover film to withstand the stresses and conditions of use. Other protective films may be applied to the cover film as a preformed sheet. For instance, adhesive-backed polyester or fluoropolymer films may be used as protective overlays. Polyester overlay films typically tend to become brittle and crack and to turn yellow when used in outside applications such as on street signs, and in some instances, may have lower optical transparency than is desired, thereby impairing the retroreflective performance of the sheeting. Furthermore, polyester films typically exhibit high dimensional memory such that when applied to irregular surfaces, e.g., over a surface having a bolt head or rivet thereon, the polyester film tends to recover and pull off the surface around the irregularity. Fluoropolymer overlay films are typically expensive. U.S. Patent No. 4,090,464 (Bishopp et al.) discloses a vandal guard sheet comprising "a sheet of clear plastic or vinyl type material" which is coated on one side with clear adhesive and is adhered to a sign. According to the reference, the sheet is secured to the underlying retroreflective sheeting with adhesive, and in some embodiments, a frame may be provided which covers the edges of the guard sheet and the sign to deter unauthorized removal of the guard sheet. The reference teaches that when graffiti is applied to the face of the guard sheet, the sheet is removed and replaced, thereby entailing a continuing cost of materials and labor for installation of new guard sheets. EP-A-0,196,154 discloses a flat transparent top coat for retroreflective sheeting which comprises a mixture of hydroxy-functional acrylic polyol and aliphatic polyfunctional isocyanate. Summary of Invention The present invention provides a durable, solvent-resistant, abrasion-resistant, and weather-resistant overlay film that may be adhered to the cover film of a retroreflective sheeting, to protect same. The surfaces of overlay films of the invention are more readily cleanable than the surfaces of many cover films currently used on retroreflective sheetings. Importantly, we have found that overlay films of the invention provide excellent resistance to graffiti such that paints, inks, and other typical graffiti materials can typically be easily and substantially completely removed from the surface of the overlay film substantially without degradation to the overlay film or its optical clarity, thereby protecting the underlying cover film and substantially preserving and maintaining the retroreflective properties of the sign of which the overlay film is a part. Furthermore, the overlay films provided herein are typically very durable and weatherable, making them well-suited for use on signs in outdoor or exposed locations. Briefly summarizing, protective overlay films of the invention are substantially transparent and comprise a durable, solvent-resistant, abrasion-resistant, and weather-resistant protective layer having an inner surface and an outer surface, and an adhesive layer on the inner surface of the protective layer, which is used to adhere the protective layer to the face of the sheeting to be protected, wherein the protective layer is made from a mixture comprising hydroxy-functional acrylic polyol and a polyfunctional curing agent, e.g., one or more of the following: polyfunctional isocyanates, aminoplast resins, azlactones, or a combination of such curing agents, further provided that said protective layer has a modulus at 2 percent elongation of at least 1380 megaPascals. Overlay films of the invention offer many advantages. They can be easily applied to signs or other substrates without sophisticated equipment, and can be applied in a factory when the retroreflective sheeting is first prepared, in a sign fabrication shop when the sheeting is converted into a sign, or in the field to existing signs. Thus, overlay films of the invention may be conveniently used on new retroreflective sign products or to upgrade or even renovate existing signs. Surface crazing and abrasions on weathered or worn retroreflective signs tend to reduce the retroreflectivity thereof, however, when an overlay film of the invention is applied thereto, these optical flaws can be filled by the adhesive layer with the protective layer providing a new smooth surface, thereby enabling more efficient retroreflection by the sign. Moreover, overlay films of the invention have good optical properties, i.e., they are substantially transparent, typically having a transmittance of 80 percent or more, and can, if desired, be made substantially colorless, such that the retroreflective brightness of a sheeting or sign to which the overlay film is adhered is substantially unhindered while the overlay protects the sheeting as discussed herein. In addition to use on retroreflective sheetings, e.g., encapsulated-lens, embedded-lens, or cube-corner sheetings, overlay films of the invention are also well suited for use on nonreflective signs and other surfaces for which protection from graffiti, dirt, etc. are desired. Brief Description of Drawing The invention will be further explained with reference to the drawing, wherein: Figure 1 is a schematic cross-section of a portion of an illustrative embodiment of a protective overly film of the invention; and Figure 2 is a schematic cross-section of a portion of a retroreflective sheeting to the cover film of which a protective overlay film of the invention has been applied. These figures, which are idealized, are not to scale and are intended to be merely illustrative and nonlimiting. Detailed Description of Invention Figure 1 illustrates in schematic cross-section a portion of typical overlay film 10 of the invention. Overlay film 10 comprises protective layer 12 and adhesive layer 14 on inner surface 13 thereof, and is shown with optional forming carrier 16 on outer surface 11 and optional release liner 18 covering adhesive layer 14. For application, release liner 18 is removed to expose adhesive layer 14 for adherence to the desired substrate (not shown). Forming carrier 16 is typically used during fabrication of overlay film 10 and may be removed at the completion of such fabrication or may be retained until application of overlay film 10 to a substrate, for instance, to protect overlay film 10 or impart greater dimension stability thereto so as to improve the handling characteristics thereof. Figure 2 illustrates in schematic cross-section a portion of an encapsulated-lens type retroreflective sheeting 20 to cover film 22 of which overlay film 10 has been adhered. Forming carrier 16 is shown being removed following application of overlay film 10 to sheeting 20. Alternatively (not shown), the forming carrier may be removed prior to application of the overlay film to the sheeting. In some instances, the forming carrier may be removed prior to application to a sign and a premask tape applied in place thereof. Such a premask tape (not shown) may possess substantial body and provide greater adhesion to the protective layer than the adhesion provided by the forming carrier, thereby enabling more convenient handling of the overlay film. Referring again to Figure 2, the embodiment of retroreflective sheeting shown therein further comprises microspheres 24 having reflectors 26, e.g., aluminum vapor coat, on the rear surfaces thereof and which are partially embedded in binder layer 28. Binder layer 28 is pushed into contact with cover film 22 in a network of intersecting bonds 30 as disclosed in the aforementioned U.S. Patent No. 3,190,178. The backside of binder layer 28 is covered with adhesive layer 32 which is used to adhere retroreflective sheeting 20 to aluminum sign panel 34. As will be understood, overlay films of the invention may also be used on other types of retroreflective sheeting than the microsphere-based encapsulated-lens sheeting illustrated herein. For example, the overlay films provided herein may be applied to the cover films of embedded-lens type sheetings or retroreflective sheetings having retroreflective elements other than microspheres with reflectors therebehind, e.g., cube-corner retroreflective sheeting. Overlay films of the invention may also be applied to nonreflective signs and other surfaces for which protection is desired. As discussed above, the protective layer of an overlay film of the invention is made from a mixture of hydroxy-functional acrylic polyol and a polyfunctional curing agent. Hydroxy-functional acrylic polyols which are useful in the present invention may be made from the following starting materials: 1) esters of methacrylic acid such as methyl methacrylate, 2) an acrylic acid ester, 3) a hydroxy-functional acrylate or methacrylate, or 4) other addition-polymerizable monomer containing a group which can be chemically converted to a hydroxyl group, either before or after incorporation into the acrylic polymer. Typically, combinations of such starting materials will be used. Optionally, the starting materials may also comprise other monomers to desirably modify the properties of the resultant polyol or ultimate protective layer in which the polyol is used. Styrene, vinyl acetate, and acrylic acid are illustrative examples of some of such monomers. The starting materials should be selected such that the resultant polyol has a T g of between -20°C and 30°C. Polyols having a T g below this range may tend to form protective layers which are undesirably soft and less abrasion- and mar-resistant, whereas those having a T g higher than the indicated range may tend to form protective layers which are undesirably brittle. For many applications, polyols having a T g between -10°C and 20°C are preferred. The starting materials should be selected such that the hydroxy equivalent weight of the resultant polyol is between 300 and 6,000, preferably between 400 and 3,000. Polyols having substantially lower hydroxy equivalent weight may tend to result in protective layers which are too brittle, whereas those having substantially higher hydroxy equivalent weight may tend to result in protective layers which are too soft. If desired, the polyol component may be a mixture of polyols, some of which have a hydroxy equivalent weight below 300 and others above 6,000, which preferably together have an effective hydroxy equivalent weight between 300 and 6,000, and an effective T g between -20°C and 30°C. If a mixture of polyols is used, the selected polyols are preferably substantially miscible or soluble with one another so as to optimize the transparency of the resultant product. "Effective hydroxy equivalent weight" is used herein to refer to the overall average hydroxy equivalent weight of the polyol component used in the present invention, whether one or more polyols are used. "Effective T g " is used herein to refer to the overall average T g of the polyol component used in the present invention, whether one or more polyols are used. If the hydroxyl content of the polyol is too high, the resultant protective layer may tend to be undesirably hydrophilic so as to become cloudy if in a damp ambient environment for an extended period. In selecting starting materials for the hydroxy-functional acrylic polyol, an acrylate having at least four carbon atoms in the ester group, such as n-butyl acrylate, is preferred as such acrylates typically tend to impart both toughness and reduced water absorption to the protective layer. To impart desired hardness, the starting materials preferably include methyl or ethyl methacrylate. To form protective layers of the present invention, one or more polyfunctional curing agents are reacted with the aforedescribed acrylic polyol. Such polyfunctional curing agents may be one or more of the following: polyfunctional isocyanates, aminoplast resins, azlactones, or a combination of such curing agents. The effective functionality of the polyfunctional curing agent is preferably between 2 and 20, and more preferably between 2 and 4. "Effective functionality" is used herein to refer to the overall average functionality of the curing agent component used in a protective film of the present invention, whether one or more curing agents are used. Curing agents with increasing functionalities tend to result in increasingly brittle protective layers, such that those curing agents having functionalities above the indicated range may tend to result in protective layers which are undesirably brittle. Polyisocyanate curing agents which are useful in the present invention include those commonly employed in polyurethane synthesis, among these being aliphatic and cycloaliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diiosocyanate and 4,4'-methylenedicyclohexyl diisocyanate; and higher polyisocyanates such as triisocyanate, for example the biuret of 1,6-hexamethylene diisocyanate, commercially available as DESMODUR N from Mobay Chemical Company and having a functionality of about 3. Because isocyanates are typically toxic, those such as 1,6-hexamethylene diisocyanate which may be volatile are preferably partially polymerized with water to form biurets of lower volatility. Other polyisocyanates which are useful for forming the protective overlay film are disclosed in U.S. Patent Nos. 3,846,378 (Griswold); 3,621,000 (Schmelzer et al.); 3,926,875 (Tsugukuni et al.); 3,993,849 (Victorius); 4,046,744 (Jenkins); and 3,694,389 (Levy). Still other useful polyisocyanates are taught by E.N. Doyle in "The Development and Use of Polyurethane Products", McGraw-Hill, Inc. (1971), at pages 93-124. Typically, overlay films of the invention are made with only limited amounts of, and preferably substantially no, aromatic isocyanates as protective layers made with such curing agents typically tend to turn yellow with time and not retain the desired high gloss. Typically, protective layers of overlay films of the invention which are made with polyfunctional isocyanate curing agents are made with from 0.5 to 1.5 equivalents of such curing agent per about 1.0 equivalent of polyol. Biurets of very high molecular weight may tend to be less compatible with the polyol, and thus may tend to impair the transparency of the resultant protective layer. Accordingly, when forming biurets, the equivalent weight should not be allowed to rise to the extent that the protective layer may suffer undesirably diminished transparency. For instance, the biuret of 1,6-hexamethylene diisocyanate may tend to be less compatible with the polyol if its equivalent weight exceeds about 200. Another technique for reducing the volatility of isocyanates is to convert them to isocyanurate trimers. As compared to biurets, the isocyanurate trimers tend to have lower viscosity. A preferred isocyanate is the isocyanurate trimer of 1,6-hexamethylene diisocyanate, described in U.S. Patent No. 4,379,905 (Stemmler et al.) and available as DESMODUR N3300 from Mobay Chemical Company. Among useful aliphatic polyfunctional isocyanates are cycloaliphatic isocyanates, such as described in U.S. Patent Nos. 4,439,370 (Zengel et al.); 4,338,256 (Fujinami et al.); and 3,912,754 (Findeisen et al.), and isocyanates which function as if they were aliphatic such as isomers of tetramethylxylylenene diisocyanate. Those isomers have aromatic rings which are not bonded directly to the isocyanate group, but are bonded to a hydrogen-free carbon atom, such as described in U.S. Patent Nos. 4,377,530 (Trenbreath et al.); and 4,379,767 (Alexanian et al.). Preferred cycloaliphatic isocyanates include 3-isocyanato-methyl-3,5,5,-trimethyl cyclohexyliso-cyanate produced by Veba-Chemie Company and dicylohexyl-methane-4,4'-diisocyanate available from Mobay Chemical Company as DESMODUR W. In addition, isocyanate-terminated polyurethane compounds and other isocyanate-functional polymers, such as isocyanate-functional acrylics, may be utilized as curing agents in protective layers of the invention. For instance, acrylic polyols may be thermally cured with one or more isocyanate-functional acrylic curing agents to form a protective layer of the invention. The preparation of isocyanate-functional acrylics is well-known in the art, and is described in U.S. Patent Nos. 4,301,257 (Zengel et al.); 3,929,744 (Wright et al.); and in the Journal of Applied Polymer Science , Vol. 20, pages 3305-3311 (1976). Furthermore, polymers which can, by known reaction techniques, be converted to isocyanate-functional polymers are also usefully employed in the present invention. For example, amine-functional polymers can be converted into isocyanate-functional polymers by the methods described in the Encyclopedia of Chemical Technology , John Wiley and Sons, New York, New York, (1981), Vol. 13, at pages 799-807. A portion of the isocyanate functionalities of the polymeric starting compound may typically be either blocked, masked, or joined to groups or moieties that can be removed by heating to control the rate of reaction, processability, and pot life of the polyol/curing agent reaction mixture. Isocyanate blocking agents are well known in the art. For instance, there can be used known blocking agents of the phenol type, lactam type, active methylene type, alcohol type, mercaptan type, acid amide type, imide type, amine type, imidazole type, urea type, carbonate type, imine type, oxime type, or sulfite type. Blocking agents of the phenol type, oxime type, lactam type, and active methylene type are used especially advantageously. Such blocking agents typically tend to decompose at lower reaction temperatures, thus making the production process more convenient. Furthermore, such blocking agents are typically less volatile, therefore, their release is less likely to cause pin holes or other discontinuities in the resultant protective layer. Specific illustrative examples of blocking agents which may be utilized in the practice of this invention are as follows: (a) Phenol type blocking agents: Phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acids, hydroxybenzoic acid esters, 2,5-di-tert-butyl-4-hydroxytoluene, etc. (b) Lactam type blocking agents: ε-Caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc. (c) Active methylene type blocking agents: Diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, t-butylacetoacetate, etc. (d) Alcohol type blocking agents: Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid esters, lactic acid, lactic acid esters, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloropropanol, ω-hydroperfluoro-alcohol, acetocyanohydrin, etc. (e) Mercaptan type blocking agents: Butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol, etc. (f) Acid amide type blocking groups: Acetoanilide, acetoanisidide, acetotoluide, acrylamide, methacrylamide, acetamide, stearylamide, benzamide, etc. (g) Imide type blocking agents: Succinimide, phthalimide, maleimide, etc. (h) Amine type blocking agents: Diphenyl amine, phenylnaphthyl amine, xylidine, N-phenylxylidine, carbazole, aniline, naphthyl amine, butyl amine, dibutyl amine, butylphenyl amine, etc. (i) Imidazole type blocking agents: Imidazole, 2-ethylimidazole, etc. (j) Urea type blocking agents: Urea, thiourea, ethylene urea, ethylene thiourea, 1,3-diphenylurea, etc. (k) Carbamate type blocking agents: Phenyl N-phenylcarbamate, 2-oxazolidone, etc. (l) Imine type blocking agents: Ethyleneimide, etc. (m) Oxime type blocking agents: Formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, diactyl monoxime, benzophenone oxime, cyclohexanone oxime, etc. (n) Sulfite type blocking agents: Sodium bisulfite, potassium bisulfite, etc. Additional isocyanate blocking agents are taught by Doyle in "The Development and Use of Polyurethane Products", supra. Preferred blocking agents for making durable, protective layers are oxime type or active methylene type blocking agents. The most preferred blocking agents are 2-butanoxime, also commonly known as methyl ethyl ketoxime, acetoxime, and diethyl malonate which are believed to offer an optimum combination of low decomposition temperature and high transparency of final product. As an alternative to employing well-known blocking agents to block the isocyanate functionality of the polymer, polymeric materials may be utilized which inherently contain masked isocyanate functionalities, which can be unmasked by heating. For example, cyclic nitrile adducts containing two or more cyclic nitrile-functional groups enter into a ring-opening addition reaction in the presence of heat and crosslinking agents to result in cured polymers containing urethane and/or urea linkages. The preparation of cyclic nitrile adducts is described in U.S. Patent Nos. 3,531,425 (Burk et al.); 3,652,507 (Burk et al.); 3,702,320 (Fritok et al.); and 4,049,007 (Russell et al.). Additionally, it is preferred that a typical urethane synthesis catalyst be used when reacting a polyfunctional isocyanate curing agent and polyol to yield the protective layer. Exemplary catalysts are disclosed by Doyle in "The Development and Use of Polyurethane Products", supra. Examples of catalysts which are typically useful include dibutyl tin dilaurate, stannous octoate, zinc naphthenate, and zinc-2-ethylhexanoate. Another class of useful polyfunctional curing agents are polyfunctional aminoplast resins, i.e., amine-aldehydes, such as urea formaldehydes and melamine formaldehydes. Urea formaldehydes are less preferred because they typically provide less durable protective layers. Examples of useful melamine resins include those having the formula: wherein R¹-R⁶ may independently be a hydrogen, or a radical of the formula -CH₂OP, wherein P is a hydrogen or an alkyl, preferably containing less than five carbon atoms. Preferably at least two of R¹-R⁶ are such a radical in order to provide good cross-linking properties. However, it is usually preferred that in each adjacent pair of functional groups, i.e., R¹ and R², R³ and R⁴, or R⁵ and R⁶, which are bonded to the same nitrogen atom, that only one of the R functionalities, i.e., R¹ or R², be such a radical and that the other R functionality be a hydrogen. Such curing agents are believed to provide faster curing reactions. Partially or fully methylated melamine resins are typically preferred aminoplast curing agents as they typically react with polyols at relatively lower reaction temperatures and provide fast cure under such conditions. Furthermore, such curing agents typically generate low amounts of volatile reaction byproducts per unit mass during cure, thereby reducing the potential for formation of pinholes in the resultant protective layer. A related class of useful curing agents are glycourils having the formula: wherein R⁷-R¹⁰ may independently be a hydrogen, or a radical of the formula -CH₂OP, wherein P is a hydrogen or an alkyl, preferably containing less than five carbon atoms. Preferably at least two of R⁷-R¹⁰ are such a radical in order to provide good cross-linking properties. When using aminoplast curing agents, the reaction mixture of polyol and curing agent preferably contains between 10 and 50, and more preferably between 20 and 30, weight percent of curing agent. When aminoplast curing agents are used to make a protective layer of the present invention, it will typically be desirable to use an acidic catalyst to speed the reaction mechanism. Examples of useful catalyst include organic phosphoric acids and organic sulphonic acids. Another class of useful polyfunctional curing agents are multifunctional azlactones. U.S. Patent No. 4,485,236 (Rasmussen et al.) discloses examples of azlactones useful as curing agents in the present invention having the formula: wherein R¹¹ is hydrogen, chlorine or a methyl group; R¹² is a single bond or a methylene or ethylene group, the last two of which can be substituted by alkyl groups having from 1 to 6 carbon atoms or phenyl groups; R¹³ and R¹⁴ are independently an alkyl or cycloalkyl group having from 1 to 12 carbon atoms, an aryl or aralkyl group having from 6 to 12 carbon atoms, or R¹³ and R¹⁴ taken together with the carbon atom to which they are bonded form a 5- to 12-membered carbocyclic ring; X is a nucleophilic group selected from and -S-, in which R¹⁶ is a hydrocarbyl group selected from (1) an alkyl or cycloalkyl group having from 1 to 18 carbon atoms, or (2) an aryl or aralkyl group having from 6 to 12 carbon atoms, R¹⁶ may optionally be substituted with at least one cyano or halo; R¹⁵ is a mono or polyvalent organic group that has a valence of n and is the residue of a nucleophilic group-substituted compound, (HX) n R¹⁵, in which X is defined above, the residue having a molecular weight up to 20,000, preferably selected from mono- and polyvalent hydrocarbyl (i.e., aliphatic and aryl compounds having 2 to 20 carbon atoms and optionally one to four catenary heteroatoms of oxygen, nitrogen or sulfur, e.g., piperazine, furan, thiophene), polyoxyalkylene, polyester, polyolefin, polyacrylate, and polysiloxane residues that can optionally all be further substituted by at least one non-nucleophilic group such as cyano, halo, ester, ether, keto, nitro, silyl, sulfide (the carbon-containing groups having up to 10 carbon atoms), and nucleophilic groups including secondary amino groups, hydroxyl groups or mercapto groups; and n is an integer having a value of 2 to 20. Optionally, R¹³, R¹⁴, and R¹⁶ can be hydrocarbons or they can be substituted by any group that does not react with the azlactone ring, such as cyano, halo, ester, alkoxy, keto, nitro silyl, and sulfide (the carbon-containing groups having up to 10 carbon atoms). When such curing agents are used in the present invention, it will typically be desirable to use a catalyst such that the polyol/curing agent reaction mixture will cure at a useful rate at a moderately elevated temperature or, in some instances, even at room temperature. Preferred catalysts for use with such curing agents include Bronsted and Lewis acid catalysts, however, weakly basic catalysts such as triethylamine, pyridine, 4-dimethylaminopyridine, and diazabicyclooctane, and strongly basic catalysts such as tetrabutylammonium hydroxide, alkali metal hydroxides, and alkali metal alkoxides may also be used. Typically, protective layers of overlay films of the invention which are made with polyfunctional azlactone curing agents are made with from 0.5 to 1.5 equivalents of such curing agent per 1.0 equivalent of polyol. We have observed, particularly in the case of protective layers made with polyfunctional isocyanate curing agents such as described herein, that protective layers having higher modulus tend to also have higher stain resistance. Accordingly, in order to provide high stain resistance, the protective layer of an overlay film of the invention should have a modulus at 2 percent elongation of at least 1380 megaPascals (200,000 pounds/inch²), and preferably at least 1900 megapascals (275,000 pound/inch²). The protective layer preferably does not soften substantially at temperatures below 50°C, or more preferably below 100°C. Protective layers which soften at Substantially lower temperatures may tend to be less resistant to penetration by solvents or dirt, and thus may, when defaced, tend to form ghosts that are difficult to clean. In some instances, protective layers made with isocyanate curing agents may contain styrene in the acrylic polyol. It is believed, based upon the discussion in D. R. Bauer and R. A. Dickie, "Cure and Photodegradation of Two-Package Acrylic/Urethane Coatings", p. 289, Ind. Eng. Chem. Prod. Res. Dev. , Vol. 25, No. 2, 1986, that incorporation of limited amounts of styrene in the polyol may improve the resistance of the resultant protective layer to photodegradation, thereby improving the weatherability of same. Limited amounts of styrene may also improve the cleanability of such protective layers. However, increasing amounts of styrene in the polyol will typically result in a substantially more brittle protective layer. Accordingly, the styrene content is preferably no more than 50 weight percent of the polyol. In most instances where the protective layer is made with a melamine resin curing agent, the protective layer is preferably substantially free of styrene as styrene may tend to reduce the weatherability of the resultant protective layer as evidenced by a substantial decrease in 60° gloss retention. If desired, the protective layer may contain limited amounts of other monomers copolymerized in the polyol to alter the properties of the resultant protective layer. For instance, acrylic acid or vinyl acetate may be incorporated in the polyol to improve the adhesion between the resultant protective layer and the adhesive layer of overlay films of the invention. Such monomers also typically tend to increase the softening point of the protective layer when incorporated therein. Higher levels of such monomers may tend to increase the hydrophilicity of the protective layer to such an extent that the protective layer may tend to absorb moisture and become foggy under damp or wet environmental conditions. Accordingly, the polyol typically comprises no more than 10 weight percent of such monomers. If desired, the protective layer may contain a coloring agent, preferably substantially transparent such as a dye, to impart desired color to the overlay film. Protective layers of the invention may also comprise one or more of the following other additives: processing aids (e.g., viscosity controlling agents, etc.), ultraviolet stabilizers, antioxidants, flow agents, leveling agents, etc. Protective layers of overlay films of the invention are typically made by casting or extruding an uncured composition upon a forming carrier and then curing the composition thereon. Examples of materials from which forming carriers may be made include polyester terephthalate, polypropylene, ethylene/acrylic acid films, and coated papers. The forming carrier provides a smooth surface upon which to form the protective layer, and may be used to protect the protective layer during fabrication, storage, or application of the overlay film as discussed with respect to Figure 1 above. If desired, the forming carrier may be removed and a premask tape or sheet applied in place thereof to facilitate handling and application of the overlay film. Because the outer surface of the protective layer is in contact with the forming carrier as the protective layer is formed, and accordingly tends to assume the surface features of the carrier, the surface of the forming carrier is preferably very smooth. The forming carrier is preferably sufficiently smooth that the outer surface of the protective layer has a 60° gloss at least 60, and more preferably at least 90, such that the overlay film will have high optical transmittance. In addition, the carrier should release from the protective layer when desired. Accordingly, depending upon the characteristics of the carrier material and the protective layer, in many instances it may be desired to apply a release agent or release treatment to the surface of the carrier. For example, in some instances, a silicone release agent may be applied to the carrier prior to forming of the protective layer thereon. In some instances, the forming carrier may also be selected with sufficient weight and thickness so as to impart sufficient body to make handling the overlay film easier. It may be preferred, however, to replace the forming carrier with a premask sheet or tape as described above. A premask tape can be optimized for desired adhesion to the protective layer and handling characteristics whereas the forming carrier is typically chosen for maximum smoothness and desired release characteristics. Protective layers of overlay films of the invention are typically between 25 to 125 µm (1-5 mils) thick, with layers from 50.8 to 76.2 µm (2-3 mils) thick typically being preferred. In some embodiments, however, overlay films may be made with protective layers having thicknesses outside these ranges in accordance with the invention. Thicker protective layers cost more and may tend to be slightly less transmissive. Protective layers substantially thinner than the indicated range are typically harder to handle and apply because they are too flimsy and, at very low thicknesses, may tend to have minute pin holes from casting or formation defects or provide insufficient protection to the cover film under mechanical stress. Protective layers between 50.8 to 76.2 µm (2 and 3 mils) thick typically provide an optimum combination of handling and performance characteristics. Following formation of the protective layer upon the forming carrier, an adhesive layer is applied, e.g., coated or laminated, to the inner surface of the protective layer. The adhesive should be substantially transparent such that it will not interfere with desired retroreflection by the underlying retroreflective sheeting. If desired, the adhesive layer may contain a coloring agent, preferably substantially transparent such as a dye, to impart desired color to the overlay film. The adhesive must provide desired adhesion to both the protective layer of the overlay film and the cover films to which overlay films of the invention are adhered. Typically, sufficient adhesion should be provided so as to resist any tendency of the protective layer to tent over surface irregularities in the cover film of the underlying retroreflective sheeting and to hinder attempts by vandals to delaminate the sheeting from the underlying cover film. In many instances, it will be preferred that the strength of the bonds of the adhesive to the inner surface of the protective layer and to the substrate to which the overlay film is applied exceed the breaking strength of the protective layer. Thus, when removal of the protective layer from a sign is attempted by a vandal, the protective layer will break into small pieces rather than permit its removal in one sheet. Furthermore, the adhesive preferably substantially retains its desired properties for the intended life of the application under probable temperature, ultraviolet radiation exposure, humidity, and other conditions. The adhesive layer should be thick enough to provide an essentially continuous coating over the entire portion of the protective layer covering the sheeting to which the overlay film is being applied, and should be kept thin enough to reduce the overall thickness of the overlay film and costs therefor. Typically, adhesive layers having thicknesses between 10 and 25 micrometers will provide the optimum combination of sufficient thickness to cover dust particles and minor surface defects in either the inner surface of the protective layer or the surface of the substrate to which the overlay film is to be adhered, and minimum thickness to reduce costs, prevent excess adhesive from oozing from rolls of overlay film, and decrease any tendency of the adhesive to reduce the transmittance of the overlay film. Typically, adhesives used in the invention will be pressure-sensitive, however, activated adhesives, e.g., heat- or microwave-activated adhesives, may be used in some embodiments. In the latter instances, the adhesive should be activatable under conditions which will not undesirably degrade the protective layer of the overlay film or the cover film or other elements of the retroreflective sheeting to which the overlay film is being applied. Depending upon the characteristics of the adhesive and the protective layer, it may be desired to prime the inner surface of the protective layer to ensure strong adhesion therebetween. Such prime, which may comprise a surface treatment or application of a priming material, should not substantially reduce the overall transmissivity of the overlay film. Examples of pressure-sensitive adhesives which are useful in overlay films of the invention include isooctyl acrylate/acrylic acid copolymers (e.g., in a 96/4 weight ratio) and urethane pressure-sensitive adhesives. U.S. Patent No. Re. 24,906 (Ulrich) discloses several pressure-sensitive adhesives which, if made in transparent form, would be useful for protective overlay films of the present invention. U.S. Patent No. 4,199,646 (Hori et al.) discloses a heat-activated, pressure-sensitive adhesive which may be used in accordance with the present invention. Typically, the adhesive layer will be covered with a release liner, e.g., a polymeric or paper film, as shown in Figure 1. In addition to covering the adhesive layer until the overlay film is applied to a sign, release liners may be coded, e.g., by color or with printed symbols or information, to facilitate classification of different embodiments of the overlay film of the invention. In most instances, depending upon their thickness and flexibility, overlay films of the invention may be cut, e.g., die cut, into sheet form or wound into roll form for storage and transport prior to use without cracking or chipping. We have discovered that the protective layers described herein are solvent-resistant, abrasion-resistant, and weather-resistant such that overlay films made using same are durable and provide effective protection to underlying retroreflective sheetings. Moreover, such overlay films, which are substantially transparent, are sufficiently hard to resist gouging or penetration such as by dirt and grit particles, etc., and yet are sufficiently conformable, i.e., flexible and extensible, that they may be adhered over irregular surfaces, e.g., corrugated or riveted panels. Furthermore, the overlay films of the invention typically exhibit sufficiently low dimensional memory that, after being shaped into a desired profile over an irregular surface, they will substantially retain the profile without tending to recover and pop off or tent, for instance, when applied over a portion of a sheeting having a bolt head or rivet protruding therefrom. The protective layers described herein provide excellent graffiti-resistance because they are resistant to solvent or ink attack. Accordingly, graffiti materials such as paints and inks applied thereto can typically be easily removed from the surface of the protective layer. Moreover, because paints and inks typically do not penetrate into the protective layer, no loss in optical properties such as clouding or coloring of the layer is suffered. Examples The invention will now be further explained with the following illustrative examples which are nonlimiting. Unless otherwise indicated, all amounts are expressed in parts by weight. The following test methods and procedures were used unless otherwise indicated. Transmittance Transmittance was determined according to ASTM D1746-70. Solvent-Resistance Solvent-resistance was evaluated by individually adhering samples of the subject protective layers to 6.9 cm by 27.9 cm (2.75 inch by 11 inch) aluminum panels and then depositing three drops of the indicated solvent to the surface of each with a 1 millilitre eyedropper. Following application of the solvent, an inverted watchglass was placed over the deposited solvent to slow evaporation thereof. The time until swelling, wrinkling, or hazing of the subject polymer was visible to the unaided eye was measured. Tensile Strength, Elongation, and Modulus Tensile strength, elongation, and modulus properties of protective overlay films were determined according to ASTM D882-67 using a subject protective layer with no adhesive thereon. Abrasion-Resistance Abrasion-resistance was evaluated by individually adhering samples of the subject protective layers to a 6.9 cm by 27.9 cm (2.75 inch by 11 inch) aluminum panel, double rubbing each by hand with a new 5.08 cm (2 inch) square piece of 000 steel wool for 50 reciprocal strokes (i.e. a single stroke being a rub in a first direction and a rub in the return direction) of equal pressure, and then wiping clean with a slightly dampened clean rag. Each sample was tested prior to and following the double rubbing for 60° gloss according to ASTM D2451-70. The percent gloss retention was determined as a measure of abrasion-resistance. Gloss Gloss was determined according to ASTM D2457-70. Weather-Resistance Weather-resistance was evaluated by measuring the 60o gloss according to ASTM D2457-70 before and after the indicated duration of accelerated weathering according to ASTM G23-81, Type E, Method 1. The percent gloss retention was determined as a measure of weather-resistance. Stain-Resistance Stain-resistance was evaluated by individually adhering samples of subject protective layers to 6.9 cm by 27.9 cm (2.75 inch by 11 inch) aluminum panels and then uniformly defacing the samples with a blue Sanford SHARPIE Brand Permanent Marker. After application of the ink, the samples were allowed to sit at room temperature for about 1 hour, and then cleaned by double rubbing using uniformly folded paper towels which had been wet with methyl ethyl ketone. Stain-resistance was evaluated by counting the number of double rubs required to clean the surface of the sample and then subjectively assessing the appearance of the sample according to the following grades: Grade Performance 1 Excellent removability, no ghosting or staining. 2 Removable, some ghosting or staining. 3 Poor removability. 4 No removability, protective layer degraded. Examples 1-3 and Comparative Examples A and B In Examples 1-3 and Comparative Examples A and B, protective layers were made as follows. A reaction mixture of the indicated polyol and aliphatic polyfunctional isocyanate was coated on a paper web which had been surface treated to provide good release properties and then passed through an oven at about 150°C for about 10 minutes to cure the protective layer. The final thickness of the protective layer was about 2 mils (50 microns). A highly tacky, acrylic pressure-sensitive adhesive was coated on the exposed surface of the protective layer to about 25 µm (microns) thickness, and then the adhesive was dried by passing through an oven at about 150°C for about 1 minute following which a silicone-treated release liner was applied over the exposed surface of the adhesive. The polyols used had the following compositions and properties; Component Polyol A Polyol B Methyl methacrylate 22.0 45.3 Butyl acrylate 30.0 41.0 Hydroxyethyl acrylate 27.0 0.0 Hydroxypropyl acrylate 0.0 13.7 Styrene 21.9 0.0 Property T g 20 -2 Equivalent Weight 600 950 In Examples 1-3 and Comparative Examples A and B, the polyol/curing agent reaction mixtures had the following compositions (expressed in equivalents): Component Examples 1 2 3 A B Polyol A 1.0 1.0 1.0 1.0 1.0 Polyol B 0.5 0.75 1.0 3.0 2.0 Isocyanate 1.5 1.75 2.0 4.0 3.0 In Examples 1-3, the isocyanate curing agent was DESMODUR N3390, tris (6-isocyanatohexamethylene) isocyanurate having an equivalent weight of about 210. In Comparative Examples A and B, the isocyanate curing agent was DESMODUR N3200, biuret of 1,6 hexamethylene diisocyanate having an equivalent weight of about 186. Comparative Examples C-E Protective overlay films were prepared in Comparative Examples C-E as in Examples 1-3, except the indicated materials were used as the protective layer. Example Material C Polyvinyl fluoride film - about 1 mil (25 microns) thick, commercially available from E.I. DuPont de Nemours and Co., as TEDLAR. D Polyester terephthalate film - biaxially orientated, about 2 mils (50 microns) thick. E Polymethylmethacrylate film - extrusion cast and biaxially orientated, about 3.0 mils (75 microns) thick. In Comparative Example E, after coating on the protective layer, the adhesive was allowed to dry at room temperature instead of being oven dried because of the oriented nature of the film. The results ofthe protective layers produced in Examples 1-3 and Comparative Examples A-E are tabulated in Table I.

Claims: A substantially transparent protective overlay film characterized in that said film comprises a solvent-resistant, abrasion-resistant, and weather-resistant protective layer having an inner surface and an outer surface, and an adhesive layer on said inner surface of said protective layer, wherein said protective layer has a modulus at 2 percent elongation of at least 1380 megaPascals and is made from a mixture of at least one hydroxy-functional acrylic polyol and at least one polyfunctional curing agent. The overlay film of claim 1 further characterized in that said acrylic polyol is made from at least one of the following: a) ester of methacrylic acid, b) ester of acrylic acid, c) hydroxy-functional acrylate or methacrylate, or d) an addition-polymerizable monomer containing a group which can be chemically converted to a hydroxyl group. The overlay film of any preceding claim further characterized in at least one of the following: a) the effective T g of said polyol is between -20°C and 30°C; or b) the effective equivalent weight of the polyol is between 300 and 6,000. The overlay film of any one of claims 1-2 further characterized in at least one of the following: a) the effective T g of said polyol is between -10°C and 20°C; or b) the effective weight of the polyol is between 400 and 3,000. The overlay film of any one of claims 1-4 further characterized in that the starting materials of said polyol comprise at least one of the following: a) at least in part an acrylate having at least four carbon atoms in the ester group; or b) one or more vinyl monomers. The overlay film of any one of claims 1-5 further characterized in at least one of the following: a) said polyfunctional curing agent comprises at least one of the following: polyfunctional isocyanate, aminoplast resin, azlactone, or a combination thereof; b) the effective functionality of said curing agent is between 2 and 20; or c) the effective functionality of said curing agent is between 2 and 4. The overlay film of claim 6 further characterized in that said film comprises a polyfunctional isocyanate curing agent wherein said curing agent comprises one or more of the following: aliphatic diisocyanate, cycloaliphatic diisocyanate, or triisocyanate. The overlay film of claim 6 further characterized in that said film comprises a polyfunctional isocyanate wherein a portion of the isocyanate functionalities of said isocyanate have blocking groups or masking groups. The overlay film of claim 8 further characterized in that said film comprises blocking groups of one or more of the following types: phenol type, lactam type, active methylene type, alcohol type, mercaptan type, acid amide type, imide type, amine type, imidazole type, urea type, carbonate type, imine type, oxime type, or sulfite type. The overlay film of claim 9 further characterized in that said blocking groups comprise one or more of the following: 2-butanoxime, acetoxime, or diethyl malonate. The overlay film of claim 10 further characterized in that the ratio of equivalents of blocking agent to equivalents of isocyanate is between 0.7 and 1.5. The overlay film of claim 6 further characterized in that said film comprises a polyfunctional isocyanate wherein said isocyanate has been converted to a biuret. The overlay film of claim 12 further characterized in that said biuret is the biuret of 1,6-hexamethylene diisocyanate. The overlay film of claim 13 further characterized in that the equivalent weight of said biuret when mixed with said polyol is less than about 200. The overlay film of claim 6 further characterized in that said curing agent comprises an isocyanate which has been converted to isocyanurate trimers. The overlay film of any one of claims 6-15 further characterized in that said protective layer comprises from 0.5 to 1.5 equivalents of said isocyanate per 1.0 equivalent of said polyol. The overlay film of any one of any preceding claim further characterized in that said film comprises a curing agent having the formula: wherein R¹-R⁶ are independently a hydrogen, or a radical of the formula -CH₂OP, wherein P is a hydrogen or an alkyl. The overlay film of claim 17 further characterized in that said curing agent is partially or fully methylated. The overlay film of any preceding claim further characterized in that said film comprises a curing agent having the formula: wherein R⁷-R¹⁰ are independently a hydrogen, or a radical of the formula -CH₂OP, wherein P is a hydrogen or an alkyl. The overlay film of any preceding claim further characterized in that said film comprises a curing agent having the formula: wherein R¹¹ is a hydrogen, chlorine, or methyl group; R¹² is a single bond or a methylene or ethylene group, the last two of which can be substituted by alkyl groups having from 1 to 6 carbon atoms or phenyl groups; R¹³ and R¹⁴ are independently an alkyl or cycloalkyl group having from 1 to 12 carbon atoms, an aryl or aralkyl group having from 6 to 12 carbon atoms, or R¹³ and R¹⁴ taken together with the carbon atom to which they are bonded form a 5- to 12-membered carbocyclic ring; X is a nucleophilic group selected from and -S-, in which R¹⁶ is a hydrocarbyl group selected from (1) an alkyl or cycloalkyl group having from 1 to 18 carbon atoms, or (2) an aryl or aralkyl group having from 6 to 12 carbon atoms, and R¹⁶ may optionally be substituted with at least one cyano or halo; R¹⁵ is a mono or polyvalent organic group having a valence of n and is the residue of a nucleophilic group-substituted compound, (HX) n R¹⁵, in which x is defined above, said residue having a molecular weight of up to about 20,000, R¹⁵ being selected from (a) an aliphatic group having from 2 to 20 carbon atoms and an aryl group having up to 20 carbon atoms, these groups optionally having 1 to 4 catenary heteroatoms of oxygen, nitrogen, or sulfur, (b) polyoxyalkylene, (c) polyester, (d) polyolefin, (e) polyacrylate, and (f) polysiloxane, all optionally including at least one non-nucleophilic or nucleophilic group; and n is an integer having a value of 2 to 20. The overlay film of any preceding claim further characterized in that said protective layer further comprises at least one of the following additives: processing aid, ultraviolet stabilizer, antioxidant, flow agent, leveling agent, cure catalyst. The overlay film of any preceding claim further characterized in that said polyol comprises limited amounts of one or more of the following: styrene, acrylic acid, or vinyl acetate. The overlay film of claim 16 further characterized in that said protective layer comprises between about 0.5 and about 1.5 equivalents of said curing agent per equivalent of said polyol. The overlay film of any preceding claim further characterized in at least one of the following: a) said protective layer has a modulus at 2 percent elongation of at least 1400 megaPascals; or b) said film has a transmittance of at least 80 percent to visible light. The overlay film of any preceding claim further characterized in that said adhesive layer comprises at least one of the following: a) a pressure-sensitive adhesive; or b) an activated adhesive. The overlay film of any preceding claim further characterized in that said film further comprises at least one of the following: a) a forming carrier or a premask tape on said outer surface of said protective layer; or b) a release liner covering said adhesive layer. A retroreflective sheeting comprising a cover film and retroreflective elements disposed behind said cover film characterized in that said sheeting further comprises the overlay film of any preceding claim adhered to the cover film of said sheeting.

Inventors: GRUNZINGER RAYMOND E C O MINNE, LEVERTY MARK W C O MINNESOTA M, GRUNZINGER, RAYMOND E. C/O MINNESOTA MINING AND, LEVERTY, MARK W. C/O MINNESOTA MINING AND
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1989
Main classification: C09J7
IPC codes: B32B27, B32B7, G09F13, B41M7, C09J7, C08K5, C08G18