Launderable retroreflective applique with colorant

Abstract: Retroreflective appliques (10) comprising a monolayer of retroreflective elements (12) partially embedded in and protruding from the front surface (14) of a binder layer (16) and an optional layer of adhesive (20) on the rear surface of the binder layer, wherein the binder layer contains a dye.

Description: Field of Invention The present invention relates to novel retroreflective appliques and articles made with such appliques. Background In order to improve safety of pedestrians, joggers, workers on roadways, etc., retroreflective markings have been attached to clothing. In one common embodiment, retroreflective appliques comprising a monolayer of retroreflective elements, e.g., transparent microspheres with hemispheric reflectors, partially embedded in a layer of binder material, with adhesive backings are bonded to articles of clothing. A problem with such appliques is that when the garment to which they are applied is laundered, a number of the retroreflective elements may be dislodged, the elements may be degraded, or the binder material may tend to discolor, e.g., turn somewhat yellow or green, resulting in undesirable discoloration of the applique. Typically, the binder layers in such appliques contain pigments such as carbon black, titanium dioxide, or flakes of metallic aluminum. In addition to imparting a desired initial coloration to the applique, these pigments serve to stabilize the color of the applique, masking discoloration of the applique when it is laundered. The pigments are sometimes referred to as a camouflage or camouflaging agent because they hide the discoloration of the binder material. In some cases, pigments provide other desired effects as well, e.g., antimony oxide imparts flame retardant characteristics to binder layers in which it is incorporated. The loadings of pigments which are necessary to achieve the desired degree of coloration stability and camouflage, e.g., often 1 weight percent or more, may tend to reduce the flexibility of the binder layer, causing the applique to be less flexible and increasing its susceptibility to loss of retroreflective elements when flexed. In some instances, the pigment may alter the characteristics of the binder material so as to interfere with adhesion of the retroreflective elements by the binder layer. During fabrication of the applique, the pigments may settle to the retroreflective element/binder material interface, further interfering with desired adhesion. In some instances, the pigment itself is degraded, e.g., aluminum flakes tend to oxidize, particularly when laundered under high pH conditions, so as to become translucent, reducing the desired camouflaging effect. As a result, some desired combinations of coloration and durability are not obtained. The problem is particularly troublesome when the clothing is subjected to industrial laundering, where the conditions of laundering are often more severe than conventional home laundering. For instance, in an industrial laundry, the laundering conditions may include wash temperatures of 40° to 90°C (105° to 190°F) and pH of 10 to 12.5, whereas in contrast, typical conditions for home laundering may include temperatures of 4° to 60°C (40° to 140°F) and pH of less than 11. Also, home laundering equipment typically subjects the articles being cleaned to less rigorous handling and stress than does industrial laundry equipment. US Patent No. 4,955,690 (Bacon, Jr.) discloses a thin caliper retroreflective transfer which can be applied to a desired substrate, e.g., a tire side wall, rubber raft, or piece of clothing, to impart a retroreflective property thereto. The transfer comprises a monolayer of retroreflective elements in a support layer. The support layer can be dual-layer, comprising a binder layer in which the retroreflective elements are partially embedded and a bonding layer, the back stratum of which is a vulcanizable elastomer. The support layer, or binder layer thereof, may comprise a whitening agent such as a pigment, e.g., titanium dioxide or a dye to increase the overall whiteness of the transfer. Alternatively, it may comprise one or more other coloring agents selected to impart a different color thereto, e.g., pigments or dyes which impart green, blue, or red color. Summary of Invention The present invention provides novel retroreflective appliques which can be applied to substrates such as fabrics and garments to impart retroreflective properties thereto. The appliques of the invention provide unexpected durability. Applied to fabric substrates, appliques of the invention exhibit surprising resistance to degradation when the article is laundered and retain a surprising degree of their coloration and retroreflective properties. In brief summary, retroreflective appliques of the invention comprise a monolayer of retroreflective elements partially embedded in and protruding from the front surface of a binder layer containing a metal-azo dye to impart coloration and camouflage properties to the binder layer. The applique may comprise an optional layer of adhesive, preferably hot melt type, on the rear surface of the binder layer. The adhesive layer is optionally covered with a removable release liner. In some embodiments, the applique is bonded to a substrate, e.g., a piece of fabric or article of clothing, with the adhesive, and in other embodiments the binder layer serves to both secure the retroreflective elements and to bond the applique to a desired substrate. If desired, the applique can be sewn onto a substrate. In an important distinction from previously known retroreflective appliques, the binder layers of appliques of the invention comprise a metal-azo dye which imparts desired coloration and camouflage properties thereto. Retroreflective appliques of the invention have been found to exhibit surprising retention of coloration and retroreflective brightness, particularly when subjected to industrial laundering conditions. As a result, articles to which appliques of the invention have been applied may be laundered many more times than previously possible while still retaining their desired coloration and retroreflective character. Brief Description of Drawing The invention will be further explained with reference to the drawing, wherein: Figure 1 is cross-sectional illustration of a portion of an illustrative embodiment of a retroreflective applique of the invention; and Figure 2 is cross-sectional illustration of a portion of another illustrative embodiment of a retroreflective applique of the invention bonded to a substrate. These figures, which are idealized, are not to scale and are intended to be merely illustrative and non-limiting. Detailed Description of Illustrative Embodiments Reference is made to Figure 1 wherein is shown an illustrative embodiment of retroreflective applique 10 of the invention. Applique 10 comprises a monolayer of retroreflective elements 12 partially embedded in and protruding from front surface 14 of binder layer 16. Disposed on rear surface 18 of binder layer 16 is optional adhesive layer 20. Applique 10 is shown with optional release liner 22 which covers the exposed surface of adhesive layer 20. To apply applique 10 to a substrate such as a fabric (not shown), release liner 22 is first removed. Applique 10 is also shown on optional temporary carrier 8 comprising paper sheet 4 and polymer lining 6. Figure 2 shows retroreflective applique 10 on substrate 30, e.g., an article of clothing such as a jacket or vest. In brief summary, a typical method of making appliques of the invention comprises arranging retroreflective elements in desired monolayer arrangement on a temporary carrier with the rear portions of the retroreflective elements presented away from the carrier, forming a binder layer over the rear portions of the retroreflective elements, and applying an optional adhesive layer on the back side of the binder layer. The most typical form of retroreflective elements 12 will be spherical microspheres 24 having reflectors 26 thereon as shown in Figure 1. As known to those skilled in the art, one method for assembling a monolayer of such retroreflective elements is to cascade microspheres onto temporary carrier 8 which secures microspheres 24 in desired arrangement temporarily. For instance, microspheres 24 can be partially embedded in heat softenable polymer layer 6 on paper sheet 4. Some examples of useful polymer coatings include polyvinyl chloride, polysulfones, polyalkylenes such as polyethylene, polypropylene, and polybutylene, polyesters such as polyethylene terephthalate, and the like. Upon cooling, polymer layer 6 retains microspheres 24 in desired arrangement. Depending in part upon the characteristics of carrier 8 and elements 12, it may be desired to condition carrier 8 and/or elements 12 to achieve desired release properties. For instance, selected release agents or adhesion promoters may be used. Microspheres 24 are typically preferably packed as closely as possible, ideally in their closest hexagonal arrangement, to achieve greater retroreflective brightness and may be so arranged by any convenient transfer process, such as printing, screening, cascading, or with a hot can roll. The most typical kind of retroreflective elements are transparent microspheres having reflectors on the rear surfaces thereof as shown in Figure 1. Such retroreflective elements typically provide satisfactory levels of retroreflective brightness over a wide range of incidence angles, i.e., the angles at which the light strikes the sheeting, a property sometimes referred to as "angularity". If transparent microspheres are used, the microspheres are preferably substantially spherical in shape in order to provide the most uniform and efficient retroreflection. Furthermore, the microspheres are preferably substantially transparent so as to minimize the amount of light absorbed by the microspheres and thereby optimize the amount of light which is retroreflected by sheetings of the invention. The microspheres are typically substantially colorless, but, may be colored to produce special effects if desired. Microspheres used herein may be made from glass or synthetic resin having the optical properties and physical characteristics taught herein. Glass microspheres are typically preferred because they typically cost less, are harder, and exhibit superior durability to microspheres made of synthetic resins. Microspheres used in the present invention will typically have an average diameter of between about 30 and about 200 microns. Microspheres which are smaller than this range may tend to provide lower levels of retroreflection because of diffraction effects, whereas microspheres larger than this range may tend to impart undesirably rough texture to the transfer or undesirably reduce the flexibility thereof. Microspheres used in the present invention will typically have a refractive index of between about 1.7 and about 2.0, the range typically considered to be useful in microsphere-based retroreflective products where, as here, the front surfaces of the microspheres are exposed or air-incident. As mentioned above, microsphere-based retroreflective elements of retroreflective transfers of the invention have reflectors on the rear surfaces thereof. Typically, such reflectors are applied to the rear surfaces of the microspheres after the microspheres have been partially embedded in the carrier, thereby facilitating the arrangement of the microspheres in substantially uniform direction for retroreflection. Furthermore, as is known, the size of reflectors, i.e., how much of the surface of the microspheres which is covered, may be controlled in part by controlling the depth into the carrier to which the microspheres are embedded prior to application of the reflectors thereto. Among the variety of materials which may be used as reflectors are vacuum-deposited or vapor-coated metal coatings, such as aluminum or silver; chemically-deposited metal coatings, such as silver; metal-coated plastic films; metal flakes; such as aluminum or silver; and dielectric coatings. Aluminum or silver coatings are typically preferred, because they tend to provide the highest retroreflective brightness. The reflective color of silver coatings is typically preferred to that of aluminum coatings, but an aluminum vapor coat is normally more preferred, because silver reflective coatings typically suffer more severe degradation in outdoor exposure than do aluminum coatings. U.S. Patent No. 3,700,305 (Bingham) discloses dielectric mirrors or coatings that may be used as reflectors in retroreflective articles of the invention. An advantage of dielectric reflectors is that appliques made with microspheres having such reflectors may be easily made in a variety of bright colors. Such reflectors are typically subject to degradation under laundering conditions, particularly industrial laundering conditions, and are accordingly used on articles destined for home laundering. Aluminum and silver reflectors typically exhibit substantially greater durability under industrial laundering conditions, but aluminum reflectors often tend to impart a gray color to the applique under ambient conditions. Following arrangement of reflective elements 12, a binder composition that forms binder layer 16 is applied thereover. Binder layer 16 is typically between about 50 and about 250 microns (2 and 10 mils) thick over the embedded portion of retroreflective elements 12, with thicknesses of between about 75 and about 100 microns (3 and 4 mils) typically being preferred. It will be understood that binder layers having thicknesses outside these ranges may be used. However, if binder layer 16 is too thin, it will not provide sufficient support to retroreflective elements 12 which will may be readily dislodged, whereas increasing the thickness of binder layer 16 leads to increased cost for applique 10 as greater amounts of the binder material are required. Also, the flexibility of applique 10 typically tends to decrease as the thickness is increased. The binder composition comprises binder material, e.g., e-beam cured materials; one or two component urethanes; nitrile rubber; acrylics; polyesters; epoxy; thermoplastic elastomers; vinyls such as polyvinyl chloride, polyvinylacetate, and their copolymers; etc., and one or more dyes. The binder composition may further comprise one or more optional components, including crosslinkers, coupling agents, and stabilizers (e.g., thermal stabilizers and antioxidants such as hindered phenols and light stabilizers such as hindered amines or ultraviolet stabilizers), flame retardants, and flow modifiers (e.g., surfactants such as fluoropolymers or silicones). In one preferred embodiment, the binder composition is an e-beam cured elastomeric material as appliques made with such materials typically provide superior performance as compared to those made with other binder materials. One useful example of e-beam curable binder materials is the HYPALON™ series of polymers, a series of chlorosulphonated polyethylenes from E.I. du Pont de Nemours & Company ("du Pont"). Such materials are highly flexible, and have been found to be resistant to degradation by exposure to ozone, oxygen, weathering, oil, and many chemicals as well as harsh laundering conditions. Illustrative examples of other e-beam curable binder materials that can be used include styrene-butadiene(isoprene)-styrene block copolymers (e.g., Shell Chemical Company's KRATON™ series), nitrile rubbers (e.g., B.F. Goodrich Company's HYCAR™ series), poly(butadiene-co-styrene), ethylene copolymers such as ethylene/vinylacetate, ethylene/acrylate, ethylene/ acrylic acid, and poly(ethylene-co-propylene-co-diene) ("EPDM") polymers. Another preferred binder material is crosslinked polyester. Illustrative examples of such materials include the VITEL™ Copolyester series from Goodyear Tire & Rubber Co. and BOSTIK™ Polyester Resin from Emhart Corp. The binder composition contains between about 0.01 and about 2.0 weight percent, preferably between about 0.1 and about 0.5 weight percent, of metal-azo dye. The dye component may be a single dye or a combination of more than one dye of selected color. Typically, black dye is preferred because it provides the most effective camouflage of discoloration of the binder material. An applique comprising microspheres with aluminum reflectors as retroreflective elements and black dye in accordance with the invention will exhibit a pleasing silver appearance. The dyes used herein are soluble in organic solvents such as methyl ethyl ketone, toluene, xylene, ethyl acetate, cyclohexanone, etc. when incorporated into the binder composition in the invention. In distinction, pigments, the conventionally used colorant in retroreflective appliques, are insoluble in such solvents. Metal-azo dyes for use in appliques of the invention are resistant to degradation or leaching out during laundering. The dyes used in the invention are superior to ionic dyes with a relatively high degree of hydrophilicity which tend to be subject to undue degradation and/or leaching during laundering. Also they are superior to dyes which are used in thermal dye transfer processes wherein they must undergo diffusion and/or sublimation under room temperature or moderately elevated temperatures and are therefore not sufficiently resistant to leaching out of the binder layer to be used herein. In general, dyes having molecular weights above about 300 will be suitable for use herein. Dyes having polar functionalities and those with amino- and hydroxyl- derivative functional groups will generally exhibit improved performance herein as compared to otherwise similar dyes lacking those or similar groups. Dyes with functional groups that would anchor to the binder material would exhibit greater resistance to diffusion out of the binder layer. Dyes which are based on heavy metal complexes typically exhibit great stability in binder layers of appliques of the invention and thus are preferred for use herein. Illustrative examples of metal-azo dyes which are useful herein include: chromium-azo dyes, e.g., ZAPON™ X50 or X51 (black), ZAPON™ Yellow 156 and 157, ZAPON™ Red 335 and 471, and ZAPON™ Violet 506, ORASOL™ CN and RL (black) and ORASOL™ Red B and Red G from Ciba-Geigy. As mentioned above, the binder composition may further comprise one or more crosslinkers. Selection of crosslinker and its amount will be dependent in part upon the elastomer which is used. Illustrative examples of crosslinkers which may be used with e-beam curable elastomers include multifunctional monomers and oligomers such as trimethylolpropanetrimethacrylate, pentaerythritol-triacrylate, and triallyl-1,3,5-triazine- 2,4,6(1H,3H,5H)trione. Illustrative examples of other useful crosslinkers include 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, neopentylglycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane ethoxy triacrylate, tris(2-hydroxethyl) isocyanurate triacrylate, dipentaerythritol pentaacrylate, urethane acrylate oligomers (e.g., CN970 series from Sartomer Co. and EBERCRYL™ from Radcure Specialties, Inc.), epoxy acrylate oligomers, and acrylic oligomers. Crosslinkers may be used alone or in combination of one or more. Typically, the binder layer will contain up to about 10 weight percent, and preferably between about 0.5 and about 2 weight percent, of such crosslinker. If too much crosslinker is used, the resultant binder layer may tend to be insufficiently flexible. Also, because many crosslinkers tend to be susceptible to degradation due to water and high pH, binder layers made with excessive amounts may tend to suffer impaired launderability. If too little crosslinker is used, the resultant binder layer may not be cured sufficiently and thus be subject to degradation, e.g., swelling and retroreflective element loss, under laundering conditions, or require high e-beam dosage to achieve sufficient cure. Typically, binder layer 16 will comprise one or more coupling agents, e.g., silane coupling agent, to promote adhesion of binder layer 16 to retroreflective elements 12. Selection of a coupling agent will be based in part upon the particular elastomer, crosslinker (if any), and retroreflective elements which are used. Illustrative examples of coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyl-tris-(2-methoxyethoxy)silane, gamma-methacryloxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexy)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, and N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane. These may be used singly or in combination. It will be understood that selection of coupling agent(s), if used, will be dependent in part upon the binder material and retroreflective elements used. To minimize fading of aluminum reflector layers, it is typically preferred that amino-containing silane coupling agents be avoided. If the binder material is a two part urethane or a isocyanate cured polyester, epoxy or methacryloxy functional silane coupling agents are preferably used and silane coupling agents containing active hydrogen moieties are preferably avoided. Gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane have been found to exhibit the best performance with chlorosulphonated polyethylenes among those listed and are preferred. The coupling agent may be applied, e.g., by spraying or coating, to the surfaces of the retroreflective elements or to the binder layer prior to its application to the elements or may be incorporated directly into the binder composition. Application to the elements provides the advantage of using lesser quantities of coupling agent, which in some instances is relatively expensive, whereas incorporation into the binder composition provides the advantage of eliminating a separate application process curing fabrication of the retroreflective applique. Typically, binder layer 16 will contain up to about 10 weight percent, and preferably between about 0.1 and about 7 weight percent, of coupling agent. If too little coupling agent is used, the resultant applique may, depending upon the characteristics of the elastomer, tend to under undesirable loss of retroreflective elements. If too much coupling agent is used, it may in some instances impair the physical properties of the binder layer, e.g., mercapto-based agents may cause the binder to swell. Also, the coupling agents are typically relatively expensive as compared to the other components of the appliques. Examples The invention will be further explained by the following illustrative examples which are intended to be non-limiting. Unless otherwise indicated, all amounts are expressed in parts by weight. Unless otherwise indicated, the following test methods were used. Retroreflective Brightness Retroreflective brightness was measured using a retroluminometer as described in U.S. defensive publication T987,003 at divergence angles of about 0.2° and entrances angles of about -4°. Laundering Launderability of appliques was evaluated by washing a piece of fabric to which the subject applique had been applied for the indicated number of cycles in a Milnor System 7 Washing Machine Model 30015M4G from Pellerin Minor Corp. using program no. 5 for medium soiled, colored fabric with the indicated detergent. Each cycle is about 40 minutes in length. The washer was loaded with about 5.5 to 6.8 kilograms (12 to 15 pounds) (dry) of laundry and used about 68 liters (18 gallons) of water at the indicated temperature. The cleaning agent used was 30 grams of FACTOR™ detergent, a detergent from Fabrilife Chemicals, Inc. containing tetrasodium pyrophosphate, nonylphenoxypoly(ethyleneoxy)ethanol, sodium carbonate, and silica. In some cases, the detergent further included 60 grams of ULTRASIL™, a pH builder from Pennwalt Corp. believed to contain 40 weight percent NaOH and 60 weight percent sodium metasilicates. CIE Color Shift The CIE Color shift, referred to herein as Delta E, was determined using the CIE tristimulus color coordinates, i.e., L, a, and b, as measured with a Minolta Chroma Meter C-121. Delta E was calculated as the square root of the sum of the squares of the changes on each of the coordinate axes in accordance with ASTM D2244-79. Example 1 Glass microspheres having an average diameter of about 40 to 90 microns were partially embedded into a temporary carrier sheet and aluminum specular reflective layers applied to the exposed portions of the microspheres to yield retroreflective elements. A binder composition comprising: Amount Component 35 Binder Material - 40 weight percent solids solution in methyl ethyl ketone of polyol based on polytetramethylene oxide having hydroxy equivalent weight of 3000; 2.23 Binder Material - 40 weight percent solids solution in methyl ethyl ketone of DESMODUR™ N-100, an aliphatic polyisocyanate adduct based on hexamethylene diisocyanate from Mobay Corp.; 0.12 Catalyst - 10 weight percent solution in methyl isobutyl ketone of dibutyl tin dilaurate; and 1.49 Dye - 10 weight percent solution in methyl isobutyl ketone of ZAPON™ X-51, a black chromium-azo dye; was coated over the retroreflective elements to a wet thickness of about 250 microns (10 mils). The applique was then wet laminated to a PRIMALUX™ fabric (an 80/20 blend of polyester and combed cotton, weight 3 ounces/yard²) from Springs Industries, Inc., and the laminate dried at 66°C (150°F) for 5 minutes then at 82°C (180°F) for 10 minutes. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. Example 2 And Comparative Example A In Comparative Example A, an array of retroreflective elements on a temporary carrier was prepared as in Example 1. A binder composition comprising: Amount Component 82.8 Binder Material - 33 weight percent solution in methyl ethyl ketone of HYPALON™ 20; 1.8 Coupling Agent - A-189, a gamma-mercapto-propyltrimethoxysilane from Union Carbide Corp.; 0.4 Crosslinker - trimethylolpropane trimethacrylate having molecular weight of 338 from Aldrich Chemical Co.; and 0.2 Pigment - 55 weight percent solution in methyl ethyl ketone of MICROLITH™ Black C-T, a carbon black pigment predispersed in modified rosin ester resin from Ciba-Geigy Corp., was coated over the retroreflective elements to a wet thickness of about 300 microns (12 mils) and dried at 66°C (150°F) for 30 minutes. The dried film was then e-beam irradiated to an exposure of 3 Mrads at 200 kilovolts to yield the binder layer. An Mrad is a megarad where a rad or "radiation absorbed dose" is equal to 100 ergs/gram. An adhesive composition comprising 100 parts of a 40 weight percent solids solution in methyl ethyl ketone of a polyol having a hydroxy equivalent weight of 3000 and 8.8 parts of DESMODUR™ CB75, a 75 weight percent solids solution in ethyl acetate of an aromatic polyisocyanate adduct based on toluene diisocyanate, from Mobay Corp. was coated over the binder layer to a wet thickness of about 200 microns (8 mils) as an adhesive layer. The applique was then wet laminated to a fabric as in Example 1. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. In Example 2, a monolayer of retroreflective elements was prepared as in Example 1. A binder composition comprising: Amount Component 100 Binder Material and Dye - solution in methyl ethyl ketone of 35 weight percent HYPALON™ 20 and 0.046 weight percent ZAPON™ X-50; 2.1 Coupling Agent - A-189; and 0.2 Crosslinker - trimethylolpropane trimethacrylate having weight average molecular weight of 338 from Aldrich Chemical Co.; was coated over the retroreflective elements to a wet thickness of about 300 microns (12 mils) and dried at 66°C (150°F) for 30 minutes. The dried film was then e-beam irradiated to an exposure of 3 Mrads at 200 kilovolts to yield the binder layer. An adhesive composition like that in Comparative Example A was then applied over the binder layer. The applique was then wet laminated to a fabric as in Example 1. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. The appliques were then evaluated by washing for the indicated number of cycles at a water temperature of about 77°C (170°F) using FACTOR™ and ULTRASIL™ cleansers. The initial retroreflective brightness of the applique in Example 2 was about 597 candela per square meter per lux and that of the applique in Comparative Example A was about 603 candela per square meter per lux. The retroreflective brightness retention results obtained are shown in Table I. After 15 laundering cycles, the applique in Comparative Example A had become yellowish gray with a Delta E of 8.6, whereas after 20 laundering cycles the applique in Example 2 was blue gray, substantially retaining its initial appearance with a Delta E of 3.6. Example 3 And Comparative Examples B And C In Example 3, an array of retroreflective elements on a temporary carrier was prepared as in Example 1. A binder composition comprising: was coated over the retroreflective elements to a wet thickness of about 250 microns (10 mils) and dried at 66°C (150°F) for 10 minutes and then at 93°C (200°F) for 5 minutes to yield the binder layer. An adhesive like that used in Example 2 was coated over the binder layer to a wet thickness of about 250 microns (10 mils). The applique was then wet laminated to a fabric as in Example 1. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. In Comparative Example B, a retroreflective applique was made and applied to a fabric as in Example 3 except the dye was replaced with about 0.5 parts carbon black and about 2.0 parts titanium dioxide pigment. In Comparative Example C, a retroreflective applique was made and applied to a fabric as in Example 3 except no colorant and no coupling agent were used. The appliques were then evaluated by washing for 25 cycles at a water temperature of about 66°C (150°F) using FACTOR™ and ULTRASIL™ cleaners. The laundering results obtained are shown in Table II. Example 4 And Comparative Example D In Example 4, an array of retroreflective elements on a temporary carrier was prepared as in Example 1. A binder composition comprising: Amount Component 100 Binder Material - 50 weight percent solids solution in methyl ethyl ketone/toluene mixture (1:1 weight ratio) of VITEL™ VPE-5545, a linear saturated polyester from Goodyear; 2.4 Binder Material - DESMODUR™ CB-75; 0.15 Catalyst - dibutyl tin dilaurate; 0.05 Dye - 10 weight percent solution in methyl isobutyl ketone of ZAPON™ X-51; and 1.5 Coupling Agent - Silane Z-6040, a gamma-glycidoxypropyltrimethoxysilane from Dow Corning Corp.; was coated over the retroreflective elements to a wet thickness of about 200 microns (8 mils). The construction was then dried by passing on a conveyer through a series of four ovens with the following temperatures and residence times: 66°C (150°F) for 1.5 minutes, 77°C (170°F) for 1.5 minutes, 77°C (170°F) for 1.5 minutes, and then 93°C (200°F) for 3 minutes, to yield the binder layer. An additional layer of the same composition was coated over the binder layer to a wet thickness of about 250 microns (10 mils). The applique was then wet laminated to a fabric as in Example 1, except the applique was dried on the fabric at 66°C (150°F) for 3 minutes and then at 93°C (200°F) for 3 minutes. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. In Comparative Example D, a retroreflective applique was made with a binder layer of the same composition as in Example 4 except the dye was omitted. The binder layer was applied with a single coating of 175 microns (7 mils) wet thickness and dried and cured at 66°C (150°F) for 2 minutes and 93°C (200°F) for 5 minutes to yield the binder layer. An additional layer of the same composition was coated over the binder layer to a wet thickness of about 175 microns (7 mils). The resultant applique was then wet laminated to a polyester fabric (S-551-060, 3.11 ounce/yard² from Milliken and Co.) and the construction dried and cured at 66°C (150°F) for 2 minutes and 93°C (200°F) for 5 minutes. The temporary carrier was then removed to reveal the silver colored retroreflective surface. The appliques were then evaluated by washing for the indicated number of cycles at a water temperature of about 74°C (165°F) using FACTOR™ and ULTRASIL™ detergents. The retroreflective brightness results obtained are shown in Table III. The initial brightness of the applique in Example 4 was 658 candela per square meter per lux and that of the applique in Comparative Example D was 578 candela per square meter per lux. After 20 laundering cycles, the applique in Example 4 was dark grayish silver in color, having undergone a Delta E of 17.7 and the applique in Comparative Example D was grayish white, having undergone a Delta E of 31.7. Example 5 An array of retroreflective elements on a temporary carrier was prepared as in Example 1. A binder composition comprising: Amount Component 350 Binder Material - 50 weight percent solids solution in methyl ethyl ketone/toluene mixture (1:1 weight ratio) of VITEL™ VPE-5545; 8.4 Binder Material - DESMODUR™ CB-75; 0.53 Catalyst - dibutyl tin dilaurate; 0.18 Dye - 10 weight percent solution in methyl isobutyl ketone of ZAPON™ X-51; and 5.4 Coupling Agent - Silane Z-6040; was coated over the retroreflective elements to a wet thickness of about 175 microns (7 mils). The construction was then dried by passing on a conveyer through a series of four ovens with the following temperatures and residence times: 66°C (150°F) for 1 minute, 77°C (170°F) for 1 minutes, 88°C (190°F) for 1 minute, and then 93°C (200°F) for 4 minutes to yield the binder layer. An additional layer of the same composition with the dye and coupling agent omitted was coated over the binder layer to a wet thickness of about 175 microns (7 mils). The applique was then wet laminated to a polyester fabric (S-551-060, a 3.11 ounces/yard² from Milliken & Co.) and the construction dried and cured on a conveyer through ovens at 66°C (150°F) for 1 minute, 82°C (180°F) for 1 minute, and 93°C (200°F) for 5 minutes. The temporary carrier was then stripped from the front of the applique to reveal the silver colored retroreflective surface. After conditioning the sample by maintaining it at a temperature of 66°C (150°F) for 7 days, the applique was evaluated by washing for the indicated number of cycles at a water temperature of about 78°C (173°F) using FACTOR™ and ULTRASIL™ cleaners. The applique had an initial retroreflective brightness of about 605 candela per square meter per lux and a retained retroreflective brightness as shown in Table IV. After 50 laundering cycles, the applique was grayish silver in color, exhibiting a Delta E of less than about 5. Example 6 and Comparative Example E In Example 6, a silver colored retroreflective applique was prepared as in Example 5, except the oven temperatures and residence times were as follows: 71°C (160°F) for 1 minute, 82°C (180°F) for 1 minute, 88°C (190°F) for 1 minute, and then 110°C (230°F) for 4 minutes. In Comparative Example E, a retroreflective applique was prepared as in Example 6, except the dye in the binder composition was replaced with 1.5 parts SILBERLINE STAMFORD™ NGH Aluminum Paste, a non-leafing, 62 to 74 weight percent solids in aromatic solvent aluminum paste from Silberline Manufacturing Co., Inc. The initial retroreflective brightnesses of the appliques were 605 and 593 candela per square meter per lux, respectively. The appliques were then evaluated for corrosion of the aluminum specular reflective layer by immersing in a 1 weight percent solution of HAMIX™ Detergent, a high pH detergent from Leverindus Nykoping, Sweden, in deionized water at 82°C (180°F) for the indicated time. The results obtained are shown in Table V below. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope of this invention.

Claims: A retroreflective applique (10) comprising a monolayer of retroreflective elements (12;24,26) partially embedded in and protruding from the front surface (14) of a binder layer (16) characterized in that said binder layer contains a metal-azo dye to impart coloration and camouflage properties to said binder layer. The applique of claim 1 further characterized in that said dye is a black dye. The applique of claim 1 or 2 further characterized in that said binder comprises between about 0.01 and about 2.0 weight percent, preferably between about 0.1 and about 0.5 weight percent, of said dye. The applique of claim 1, 2 or 3 further characterized in that said binder layer comprises at least one of the following binder materials: e-beam curable elastomer; one or two component urethane; nitrile rubber; acrylic; polyester; epoxy; thermoplastic elastomer; and vinyl. The applique of either of claims 1, 2, 3 and 4 further characterized in that said binder layer further comprises at least one of the following: crosslinkers, coupling agent, stabilizer, flame retardant, and flow modifier. The applique of claim 5 further characterized in that said crosslinker comprises one or more of the following: trimethylolpropanetrimethacrylate, pentaerythritol-triacrylate, triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)trione, 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, neopentylglycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane ethoxy triacrylate, tris(2-hydroxethyl) isocyanurate triacrylate, dipentaerythritol pentaacrylate, urethane acrylate oligomer, epoxy acrylate oligomer, and acrylic oligomer. The applique of claim 5 or 6 further characterized in that said coupling agent comprises one or more of the following: vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyl-tris-(2-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexy)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, and N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane. The applique of any one of claims 1 to 7 characterised in that said applique further comprises a layer of adhesive (20) on the rear surface of said binder layer. The applique of claim 8 further characterized in that said adhesive is a hot melt adhesive. The applique of claim 8 or 9 further characterized in that said applique is bonded to a fabric with said adhesive. The applique of any one of claims 1 to 10 further characterised in that said retroreflective elements comprise microspheres (24) with hemispheric reflectors thereon (26). The applique of claim 11 further characterized in that said reflectors comprise vapor-coated aluminum.

Inventors: LI WU-SHYONG, LI, WU-SHYONG, LI, WU-SHYONG, C/O MINNESOTA MINING AND
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1992
Main classification: G02B5
IPC codes: B44C5, B32B3, A44C3, E01F9, D03D15, C08J3, A41D13, A41D31, G02B5