MXPA99009103A - Laminate of transfer term - Google Patents

Abstract

This invention relates to a thermal transfer laminate, including: a face block including a first layer having an upper surface and a lower surface, a heat-activatable adhesive layer underlying the lower surface of said first layer; of adhesion coating the upper surface of said first layer, a transparent coating layer resistant to abrasion coating said adhesion promoter layer, and another adhesive layer coating said abrasion resistant coating layer. In one embodiment, an ink or graphics layer covers the upper surface of the first layer of the face block and provides a pictorial design and / or a printed message. In one embodiment, the laminate is attached to a support layer. In one embodiment, the laminate adheres to a substrate such as an interior automotive surface.

Description

THERMAL TRANSFER LAMINATE Technical Field This invention relates to thermal transfer laminates. Such thermal transfer laminates are useful in providing pictorial and / or printed designs or messages (eg, labels, decals, etc.) adhered to substrates (eg, metal, plastic, leather, paper or textile substrates) such as surfaces automobile interiors (for example, seatbelts, sun visors, instrument panels, headrests, seat backrests, door panels, and the like). BACKGROUND OF THE INVENTION Thermal transfer laminates are used in automotive interiors to provide instruction and / or warning labels on safety belts, visors, dashboards and the like. A typical construction of such laminates is illustrated in Figure 1. With reference to Figure 1, a thermal transfer laminate 10 has a paper backing 12 and a release liner 14 adhered to one side of the paper backing 12. A layer of ink or graphics 16 is adhered to the release liner 14 and a heat-activatable adhesive layer 18 is adhered to the graphics layer 16. The laminate 10 is placed on the substrate 20 (eg, safety belt, visor, etc.) with the adhesive layer 18 in contact with the substrate 20. The heat and pressure is applied to the laminate 10 through the paper support 12 to heat-seal the laminate 10 to the substrate 20. The paper support 12 is removed after the heat-sealed lamination. The release liner 14 is separated with the paper backing 12. The ink or graphics layer 16 and the adhesive layer 18 remain adhered to the substrate 20. Such thermal transfer laminates have a number of disadvantages. These include the fact that the ink or graphics layer 16 can not be seen through the paper support 12 during the application of the laminate 10 to the substrate 20. This may result in an im-precise placement of the ink layer or graphics 16 on the substrate 20. The ink or graphics layer 16 applied to the substrate 20 tends to adapt to the surface contours of the substrate 20 and when the surface is not smooth (eg, when the substrate 20 is a polyester material). with foam reinforcement for automobile interior), the pictorial design and / or the printed message provided by the ink layer or graphics, often appears blurred or out of focus. Once applied to the substrate 20, the ink or graphic layer 16 tends to have poor characteristics of chemical resistance and durability (e.g., poor abrasion resistance), and low opacity. These problems are overcome with the thermal transfer laminates of the invention. SUMMARY OF THE INVENTION This invention relates to a thermal transfer laminate, comprising: a face block including a first layer having an upper surface and a lower surface, and a removable adhesive layer underlying the lower surface of said layer. first layer; an adhesion promoter layer coating the upper surface of said first layer; a transparent abrasion resistant coating layer covering said adhesion promoter layer; and another adhesive layer coating said abrasion resistant coating layer. In one embodiment, a layer of ink or graphics is placed between the adhesion promoter layer and the abrasion-resistant transparent coating layer, and provides a pictorial and / or printed message or design. In one embodiment, the laminate adheres to a backing sheet. In one embodiment, the laminate is adhered to a substrate such as an interior surface of an automobile. BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings, analogous references indicate analogous parts or features. Figure 1 is a schematic illustration of the side of a thermal transfer laminate of the prior art, the laminate being sealed to a substrate. Figure 2 is a schematic illustration of the side view of a thermal transfer laminate embodying the present invention in a particular form. Figure 3 is a schematic illustration of the side view of an alternative embodiment of the thermal transfer laminate of the present invention. Figure 4 is a schematic illustration of the side view of another embodiment of the thermal transfer laminate of the present invention. Figure 5 is a schematic illustration showing the thermal transfer laminate of Figure 4 being adhered to a substrate. Figure 6 is a schematic illustration showing the thermal transfer laminate of Figure 4 adhered to a substrate, the support sheet being removed from the laminate. DESCRIPTION OF THE PREFERRED EMBODIMENTS With reference to Figure 2, the thermal transfer laminate of the invention, in one of its illustrative embodiments, is generally indicated with the reference numeral 100, and is composed of: a face block 110 which includes a first layer 112 having an upper surface 114 and a lower surface 116, and a heat-activatable adhesive layer 118 underlying the surface 116; an ink layer or graphics 120 in the form of a monochrome or multicolored printed message, pictorial design, or their combination, covering the upper surface 114; an adhesion promoter layer 130 overlying the ink layer 120; an abrasion-resistant transparent coating layer 140 coating the adhesion promoter layer 130; another adhesive layer 150 coating the abrasion resistant coating layer 140; and a backing sheet 160 adhered to the adhesive layer 150. An alternative embodiment of the thermal transfer laminate of the invention is illustrated in Figure 3. In this alternative embodiment, the thermal transfer laminate 200 is the same as the laminate. of thermal transfer 100 illustrated in Figure 2, except that the thermal transfer laminate 200 uses a different face block, namely, the face block 210. The face block 210 is composed of a central thermoplastic layer 212 having an upper surface 214 and a lower surface 216. A top optic plastic film layer 220 is adhered to the upper surface 214 of the central layer 212. The lower surface 217 of the film layer 220 is in contact with the surface upper 214 of the central layer 212. The upper surface 222 of the film layer 220 is a printable surface. The thermoactivatable adhesive layer 230 is adhered to the lower surface 216 of the core layer 212. The remaining portions of the thermal transfer laminate 200 are the same as the equal number portions of the heat transfer laminate 100. That is, the layer of ink or graphics 120 covers the upper surface 222; an adhesion promoter layer 130 overlies the ink layer 120; an abrasion-resistant transparent coating layer 140 covers the adhesion promoter layer 130; the adhesive layer 150 covers the transparent abrasion-resistant coating layer 140; and a support sheet 160 is adhered to the adhesive layer 150. The heat transfer laminate 200A illustrated in Figure 4 is identical to the heat transfer laminate 200 illustrated in Figure 3, with the exception that the thermal transfer laminate 200A it includes another adhesion promoter layer 135 positioned between the upper surface 222 of the film layer 220 and the ink layer or graphics 120. In all other respects the thermal transfer laminates 200 and 200A are identical. In one embodiment, the upper surface 114 of the first layer 112 and the upper surface 222 of the film layer 220 are subjected to corona treatment to raise the surface energy of such surfaces to allow improved printing on such surfaces. The corona treatment consists of discharging up to approximately 10,000 volts of electricity from a ceramic electrode to a ground roll on which the film passes. Said high-voltage field called "corona" alters the surface of the film. The treatment of the surface of the film raises the surface energy of the film (measured in terms of the dyne level) and allows an improved impression. Face blocks 110 and 210 typically have general thicknesses of about 0.0254 to about 0.635 mm (1 to 25 mils), and in an embodiment of about 0.0254 to about 0.508 mm (1 to 20 mils) , and in one embodiment from about 0.00254 to about 0.381 mm (1 to 15 mils), and in one embodiment from about 0.0254 to about 0.254 mm (1 to 10 mils), and in one embodiment from about 0.0508 to about 0.177 mm (2 to 7 mils), and in one embodiment from about 0.076 to about 0.127 mm (3 to 5 mils). The thickness of the thermosetting adhesive layers 118 and 230 is in the range of about 0.0025 to about 0.254 mm (0.1 to 10 mils), and in an embodiment of about 0.0025 to about 0.127 mm (0.0005 in). , 1 to 5 thousandths of an inch), and in an embodiment of about 0, 00076 to approximately 0.0508 mm (0.3 to 2 mils). The central layer 212 has a thickness of about 10o to about 90? from the face block 210, and in an embodiment from about 20% to about 80%, and in an embodiment from about 30% to about 70%, and in an embodiment from about 402 to about 60%, constituting the combined thicknesses of the layers 220 and 230 the rest of the thickness. The thicknesses of the layers 220 and 230 may be identical or different. In one embodiment, the thickness of the film layer 220 / core layer 212 / heat-activatable adhesive layer 230 is 103/80-V10%, and in one embodiment 15% / 70V15%, and in one embodiment of 20 ^ / 60 ^ / twenty . In one embodiment, the ratio is 10% / 60% / 30%. In general, relatively thin thermoactivatable adhesive layers are preferred for cost reasons. However, relatively thick layers are often required when the substrate to which the heat transfer laminate is to adhere is relatively rough and porous (eg, a finished fabric substrate). The first layer 112. and the central layer 212 may be composed of metal foil, polymer film, sheet of paper or combinations thereof. Said layers may be composed of textiles including woven and non-woven fabrics made of natural or synthetic fibers. Said layers may be films or sheets of a single layer or they may be multi-layer constructions. These include polymer films and multi-layer polymer films. Multilayer constructions and multilayer polymer films have two or more layers, and in one embodiment from about two to about seven layers, and in one embodiment from about three to about five layers. The layers of such films and multilayer constructions may have the same composition and / or size or may be different. The metal sheets include sheets of metals such as copper, gold, silver, tin, chromium, zinc, nickel, platinum, palladium, iron, aluminum, steel, lead, brass, bronze and alloys of the previous metals. Examples of such alloys include copper / zinc, copper / silver, copper / tin / zinc, copper / phosphorus, ero-mo / molybdenum, nickel / chromium, nickel / phosphorus and the like. The metal foils can be used alone or can be used or adhered to a palmate film or sheet to form a multi-layered construction or laminate. Polymeric films include polyolefins (linear or branched), polyamides, polystyrenes, nylon, polyesters, polyester copolymers, polyurethanes, polystyrene, styrene-maleic anhydride copolymers, copolymer = styrene-acryltromethyl, of sodium or zinc salts of ethylene-methacrylic acid, po-methyl methacrylates, cellulosics, acrylic polymers and copolymers, polycarbonates, polyacryloyl thioles and ethylene-vinyl acetate copolymers. Acrylates such as citrate and lenmetacrylic, ethylene methyl acrylate, ethylene acrylic acid and ethylene ethyl acrylate are included in this group. Further, this group includes polymers and copolymers of olefin monomers having, for example, from 2 to about 12 carbon atoms, and in one embodiment from about 2 to about 8 carbon atoms. These include the α-olefin polymers having from 2 to about 4 carbon atoms per molecule. These include polyethylene, polypropylene, poly-1-butene, etc. An example of a copolymer within the above definition is a copolymer of ethylene with 1-butene having from about 1 to about 10 weight percent of the l-butene comonomer incorporated in the copolymer molecule. The polyethylenes that are useful have various densities including low, medium and high density bands. The low density band is from about 0.910 to about 0.925 g / cm * 5; the average density band is from about 0.925 to about 0.940 q / cm1; and the high density band is from about 0.940 to about 0.965 g / cpr. An example of a commercially available material that is useful can be obtained from Du Pont under the trade name Mylar LB; this material is identified as a biaxially oriented polyester film. Also useful are films prepared from mixtures of copolymers or mixtures of copolymers with homopolymers. The films can be extruded as monolayer films or multi-layer films. The films can be oriented movies or non-oriented movies. Paper sheets include paper, clay-loaded paper, glassine, straw, bark, cotton, linen, corn stalks, sugarcane, bagasse, bamboo, hemp and similar cellulose materials prepared by processes such as the processes of soda, sulphite or sulphate (Kraft), the neutral sulfite firing process, the alkali-chlorine processes, nitric acid processes, semi-chemical processes, etc. Although paper of any basis weight can be used, paper having basis weights of the order of from about 20 to about 150 pounds per ream (lb / ream) is useful, and papers having weights of the order of about 30 to about 60 lb / ream. The layers 112 and 212 may be composed of a polymer-coated paper that is basically a sheet of paper that is coated on one or both sides with a polymer coating. The polymeric coating, which may consist of high, medium or low density polyethylene, polypropylene, polyester and other similar polymeric films, is coated on the paper surface to increase strength and / or dimensional stability. The weight of these types of coated paper blocks can vary over a wide range, and weights of the order of about 5 to about 50 lb / ream are useful. In total, the final coated paper layer may consist of between about 10o and about 40'e by weight of polymer. For two-sided coatings, the amount of polymer is ordinarily roughly divided between the top and bottom surface of the paper. The thermoactivatable adhesive layers 118 and 120 can be made from thermoplastic film materials or heat activatable adhesives. These include polyolefins (linear or branched), polyaids such as nylon, polyester copolymers, sodium or zinc salt based ethylene-methacrylic acid-based lonomers, polyacrylonitriles, and ethylene-vinyol acetate copolymers. Included in this group are acrylates such as ethylene methacrylic acid, ethylene methyl acrylate, ethylene acrylic acid and ethylene ethyl acrylate. Also included in this group are polymers and copolymers of olefin monomers having, for example, from 2 to about 12 carbon atoms, and in one embodiment from 2 to about 8 carbon atoms. These include the α-olefin polymers having from 2 to about 4 carbon atoms per molecule. These include polyethylene, polypropylene, poly-1-butene, etc. An example of a copolymer within the above definition is a copolymer of ethylene with 1-butene of from about 1 to about 10 weight percent of the 1-butene comonomer incorporated in the copolymer molecule. Polyolefins include amorphous polyolefins. Polyethylene = which are useful have various densities including the low, medium and high density bands defined above. The ethylene / methyl acrylate copolymers obtainable from Chevron under the trade name EMAC can be used. These include EMAC 2260, which has a methyl acrylate content of 2% by weight and a melt index of 2.0 grams / 10 minutes @ 190 ° C, 2.16 kg; and EMAC SP 2268T, which also has a methyl acuplate content of 24% by weight and a melt ion of 10 qramos / 10 minutes @ 190 ° C2.16 g. Polymeric film materials prepared from mixtures of copolymers or mixtures of copolymers with homopolymers are also useful. The film layer 220 is composed of thermoplastic film materials selected to obtain ink printable surfaces that provide stable printing of good quality. Exemplary thermoplastics which may be used alone or in combination include polyolefins such as polyethylene, polypropylene and polybutylene, thermoplastic polyesters, polyamides such as "Nylon, acrylic copolymers such as polyethylene methacrylic acid, polyethylene ethyl acrylate and polyethylene methyl acrylate, polystyrene, polyurethane, polycarbonate, polyacrylonitriles, ethylene-propylene copolymers, etc. The choice of material for the film layer 220 is determined by the properties desired for said layer such as improved primiibility, weathering, etc. The choice of ateal for the film layer 220 also depends on the material used for the heat-activatable adhesive layer 230 if the layers 220 and 230 are to be wound on one another. When the layers 220 and 230 are wound on one another, blocking on the roller is a problem especially if the roller can be exposed to heat during storage or transport. In one embodiment, the ethylene vmyl acetate copolymer (EVA) and polyolefin mixtures with EVA are useful materials for the film layer 220. For a good immunity, the EVA content of the mixture should be greater than about 10? by weight, and in one embodiment between about 20% and about 80%, and in one embodiment from about 30% to about 70%. Although the EVA content may be higher, the polyolefin is the least expensive component. In addition, the higher contents of EVA tend to make films more prone to blocking problems. The vinyl acetate content of the EVA copolymers can be of the order of about 5? at about 25o. US 631-04, which is an ethylene vmyl acetate copolymer having a vinyl acetate content of 19% by weight and can be obtained from Quantum Chemical, is an example of a commercially available copolymer that can be used. The olefin polymer of the polyolefin-a-VA mixtures may be alpha-olefin polymers and copolymers such as ethylene, propylene. Examples of such polymers and copolymers include polyethylene, polypropylene, copolymers of ethylene and propylene, blends of polyethylene and / or polypropylene with ethylene-propylene copolymers, etc. A commercial example is WRD 51057, which is a Union Carbide product identified as a polypropylene homopolymer. Layers 112 and 212 may have a light appearance or may be pigmented. Pigments that can be used include titanium dioxide, both rutile crystal structure and anatase. In one embodiment, the pigment is added to the core layer material in the form of a concentrate containing the pigment and a re-syring vehicle. The concentrate may contain, for example, from about 20% to about 80% by weight of pigment, and from about 20% to about 80% by weight of ream vehicle. The resin carrier may be any thermoplastic polymer having a melting point on the order of about 100 ° C to about 265 ° C. Examples include polyethylene, polypropylene, polybutylene, polyester, nylon and the like. In one embodiment, a concentrate of titanium dioxide is used which is composed of a mixture of about 30-a to about 70% by weight of polypropylene and from about 70% to about 30% by weight of titanium dioxide. An example of a commercially available pigment concentrate that can be used can be obtained from A. Schul an Inc., under the trade name PoylBatch White P8555 SD, which is identified as a white concentrate having a Rutile titanium dioxide concentration coated 50% by weight in a homopolymer polypropylene vehicle resin. Another example is Ampacet 110233 which is a product of Ñ pacet Corporation identified as a Ti02 concentrate containing 50% T? 02 rutile and 50% low density polyethylene. The concentration of pigment in the central layers 112 and 212 can be up to about 25% by weight, and when used, is generally in the range of about 5% to about 25% by weight., and in an embodiment from about 10% to about 20% by weight. Layers 112 and 212 may include a filler material to increase opacity. The fillers that can be used include calcium carbonate and talc. In one embodiment, the filler is added to the core layer material in the form of a concentrate containing the filler and a ream vehicle. The concentrate may contain, for example, from about 20% to about 80% by weight of filler, and from about 20% to about 80% by weight of beef vehicle. The resin vehicle can be any thermoplastic polymer having a melting point in the range of about 100 ° C to about 265 ° C. Examples include polyethylene, polypropylene, polybutylene, poly-ether, nylon and the like. Also included are thermoplastic copolymers such as ethylene methyl acrylate, and the like. In one embodiment, a calcium carbonate concentrate consisting of a blend of about 50% to about 80% by weight of polypropylene and from about 20% to about 50% by weight of calcium carbonate is used. An example of a commercially available pigment concentrate that can be used, can be obtained from A. Schulmann Inc., under the commercial designation PF 920, which is identified as a calcium carbonate concentrate having a concentration of calcium carbonate. 40% by weight in a polypropylene homopolymer vehicle resin. Another example is Ampacet 101087, which is a product of Ampacet Corporation identified as a calcium carbonate concentrate containing 30% by weight of calcium carbonate and 70% by weight of ethylene methyl acrylate. The concentration of filler in layers 112 and 212 can be up to about 40% by weight, and when used, is generally in the range of about 10% to about 40% by weight, and in an embodiment of about 10% by weight. about 35% by weight. Layers 112, 118, 212, 220, and 230 may contain ultraviolet (UV) light absorbers or other light stabilizers. . Such additives are included to avoid degradation due to sunlight. A useful type of stabilizer is a hindered amine light stabilizer. Stabilized amine light stabilizers are described in the literature such as in U.S. Patent 4,721,531, columns 4 to 9, which is incorporated herein by reference. Stabilized amine light stabilizers can be, for example, derivatives of 2,2, 6, 6-tetraalkyl pipelines or substituted piperizindiones. Various bonded amine light stabilizers useful in the invention can be obtained commercially, for example, from Ciba-Geigy Corporation under the general trade names "Tinuvin" and "Chemisororb", and from Cytec under the general designation "Cya - sorb-UV ". Examples include Tinuvm 111 which is identified as a mixture of 1, 3, 5-triazine-2,4,6-triamna, N, N ", - [1,2-ethanodnlbis [[[4,6 -bis [butyl (1, 2, 2, 6, 6-pentamet? l-4-piperidin? l) amino] -1, 3, 5-tpazin-2-yl] mmo] -3, 1 propanediyl]] - bis [N ', N "-dibutyl-N', N" -bis (1,2,2,6,6-pentamethyl-4 piperidinyl.) and dimethyl succinate polymer with 4-hydrox? -2 , 2, 6, 6, -tetramet? L- 1- piperidinetanol; Tinuv 123 which is identified as bis- (1-octyllox? -2,6,6-tetramethyl-4? Ipepdin? L) sebacate; Tinuvm 770 which is identified as bis-2,2,6,6-tetramethyl-4-piperidinyl) -sebacate; Tinuvm 765 which is identified as bis- (1, 2, 2, 6, 6-pentamet? L-4-p? Per din? L) -sebacate; T uvin 622 which is a polyol of succinate of dimethyl with 4-hydroxy-2, 2, 6, 6, -tetramethi-1-piper? dmetanol; and Chemassorb 944 which is poly [[6- (1, 1,3, 3-tetramethyl-butyl) ammo] -l, 3,5-triazine-2,4-d? il] [[2,2,6] 6-tetramethyl-4-piperidyl) imino]] hexamethylene (2,2,6,6-tetramet? L-4-p perid? L) i ino] 3, and Chemassorb 119 which is identified co or 1, 3, 5-triazine-2, 6-triamine N ', N "- [1,2-ethanedisbis [[[4,6-b? S [butyl (1,2, 2,?, 6-pentamethyl- 4- peperidinyl) amino] -1,3,5-triazm-2] yl]? Mmo] -3,1-propanoyl]] -bis [N ', N "-dibutyl-N *, N" -b? s (1, 2, 2, 6, 6-pentamethyl-4? -per? diml) - UV absorbers include those obtainable from Ciba-Geigy ba or the name Tinuv and Great Lakes Chemical Corporation under the commercial designation "Lowilite." Examples include: Tinuv P, which is identified as co or 2- (2'-hydro? i-5'-met? l-phenyl) -benzotriazole; Tinuvin 326, which is identified as 2- (3'-tert-butyl-2 * -hydro-5'-methylphenyl) -5-chlorobenzo-triazole; Tinuvm 238, which is identified as 2- (2'h? Drox? -3 ', 5' -di-tert-amylphenyl) benzotriazole; lo ili-te 20, which was identified a as 2-hydroxy-4-methoxy-benzophenone; The ilite 22, which is identified as 2-hydrox? -4-n-octo ?? - benzophenone; and Lowilite 1200, which is identified as 2-hydroxy-4-n-dodecyloxy-benzophenone. A useful stabilizer can be obtained under the trade name Ampacet 10561 which is an Ampacet product identified as a UV stabilizing concentrate containing 20% by weight of a UV stabilizer and 80% by weight of a low density polyethylene carrier resin. The concentration of UV absorber or light stabilizer can be up to about 2,% by weight, and in one embodiment is about 0.05% to about 1% by weight. The heat-activatable adhesive layer 118 generally has a lower melting point than any of the other layers used in the heat transfer laminate 100 so that the layer 118 can function as heat-activatable adhesives. Similarly, the heat-activatable adhesive layer 230 generally has a lower melting point than any of the other film layers used in the thermal transfer laminate 200 or 200A. Typically, the melting points determined by differential scanning colopmetry in the second thermal cycle of the thermoactive adhesive layers 118 and 230 are of the order of about 50 ° C to about 150 ° C, and in an embodiment of about 70 ° C to about S5 ° C. The melting point of the thermoactivable adhesive layer 118 is typically at least about 10 ° C lower than the melting point of the core layer 112, and in one embodiment is about 86 ° C lower. The melting point of the heat-activatable adhesive layer 230 is typically at least about 10 ° C lower than the melting point of the core layer 212, and in one embodiment is about 86 ° C lower. In embodiments where the thermal transfer laminate is to be attached to a rough or porous substrate (eg, a woven fabric), it is preferred that the heat-activatable adhesive layer 118 or 230 be relatively thick and that the difference between the melting point of the central layer 112 or 212 and the melting point of the corresponding co-operating adhesive layer 118 or 230 is as high as possible. This provides the thermal transfer laminate of the invention with the advantage of preventing or reducing the rough or porous surface of the substrate from appearing through the laminate to provide a clear and precise pictorial design and / or a printed message instead of an image of Blurry or out of focus. The layers 112, 118, 212, 220 and / or 230 may contain a slip additive. These include primary amides such as stearamide, behena ida, olea ida, eruca-mide and the like; secondary amides such as stearyl erucamide, erucyl erucamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide and the like; ethylene bisa-mides such as N, N'-ethylenebistearamide, N, N'-ethylenebisol and analogous; and combinations of two or more of the above amides. An example of a useful slip additive can be obtained from Ampacet under the trade name 10061; this product is identified as a concentrate containing 6% by weight of a stearamide slip additive. The slip additive can be used in a concentration of the order of up to about% by weight, and in an embodiment of about 0.05% to about 2% by weight, and in an embodiment of about 0.1 to about 0. , 5% by weight. The layers 112, 118, 212, 220 and / or 230 may contain an anti-blocking additive. These include natural silica, diatomaceous earth, synthetic silica, glass spheres, ceramic particles, calcium carbonate particles, calcium silicate particles, fatty amide particles, aluminum silicate and the like. Examples of available anti-blocking additives include those obtainable from A. Schulman under the trade designation CABL 4040 which is identified as solid pellets containing 5% silicate, 5% ceramic microspheres and the balance being a low density polyethylene. Also Schulman AB5, which is an anti-blocking concentrate obtainable from A. Schulman, which includes 5% synthetic solid amorphous silica in 95% high density polyethylene, can be used. Polybatch F-20, which can be obtained from A. Schulraan, can be used and is identified as a concentrate containing 20% natural silica based on low density polyethylene. Other useful additives include those obtainable from Zeelan Industries under the trade designation Zeeospheres; 3M under the trade designation Scotchlite Glass Bubbles; Potters Industries under the commercial designation Sphepglass; Mo-_ Sci Corporation under the trade designation Precision Glass Spheres (Class IV); Huber under the commercial designation Huber Q; Nyco erals ba or the Nycor, Nyad, Ultrafibe, Pri glos, Nyglos and Wallastocoat commercial designation; Jayco under the trade designation Dragonite; Witco under the commercial designation Kenamide; and U.S. SiLica under the commercial designation Min-U-Sil. The anti-blocking additive can be used in a concentration of up to about 202 by weight, and in an embodiment of from about 0.1% to about 10% by weight, and in an embodiment of from about 0.1% to about 5% by weight. The antiblocking and sliding additives can be added together in the form of a resin concentrate.

An example of such a concentrate can be obtained from DuPont under the trade designation Elvax CE9619-1. Said beef concentrate contains 20% by weight of silica, 7% by weight of an amide slip additive, and 73% by weight of Elvax 3170 (product of DuPont identified as ethylene / vinyl acetate copolymer having a content of vinyl acetate of 18 $ in weight). The amount of antiblocking and sliding additives can be identical or different in each layer. In general, it is desirable to minimize the amount of said additives to avoid problems of ink adhesion and low bonding of the term seal. However, an amount sufficient to prevent blocking of self-wound film rolls is usually desirable. The layers 112, 118, 212, 220 and / or 230 may contain a secondary amount of an adhesive material to improve the adhesion of the layers 112 and 118 to each other, or the layers 220 and / or 230 to the central layer 212. In addition , or alternatively, the adhesive bonding layers can be placed between the film layers 112 and 118, or between the core layer 212 and one or both of the film layers 220 and 230 to improve adhesion. The adhesive material may consist of an adhesive ream such as ethylene / vmyl acetate copolymer. These include DuPont Elvax 3170 and 3190LG. Adhesive adhesives that can be obtained from DuPont ba or the Bynel trade designation can also be used. When included in the central layer 212, the adhesive resin is used in a concentration of up to about 401 by weight, and in an embodiment of about 53. to about 25% by weight. When used in layers 112, 118, 220 and / or 230, the adhesive material is used in a concentration of up to about 100% by weight, and in an embodiment of about 45% to about 85% by weight. When used in the form of a layer or layers of film between the film layers 112 and 118, or between the core layer 212 and the film layers 220 and 230, each of such layer or layers of adhesive resin film has a thickness of about 5% to about 40 l of the thickness of the overall face block 110 or 210, and in an embodiment of about 10% to about 25%. The face blocks 110 and 210 can be made using a polymer co-extrusion process. The coextrudate of polymeric film materials is formed by the simultaneous extrusion of two or more extruders = and a suitable known extrusion die type, whereby the layers 112 and 118, or the core layer 212 and the film layers 220 and 230 adhere to each other in a permanently combined state to obtain a unitary coextrudate. As indicated above, a bonding layer or layers of an adhesive ream can be included in the face blocks 110 and 210 and such a tie layer or layers can be co-extruded with the face blocks 110 and 210. Alternatively, it can be using an extrusion coating process to lay one or more layers on a moving sheet. The processes for making such face blocks are known in the art. The ink or graphics layer 120 is an onocolor or multicolored ink layer, depending on the printed message and / or the pictorial design provided for the thermal transfer laminate. These include variable printed data such as serial numbers, bar codes and the like. The thickness of the ink layer is typically in the range of about 0.5 to about 5 microns, and in an embodiment of about 1 to about 4 microns, and in an embodiment of about 3 microns. The inks used in the ink layer 120 are preferably water-based, solvent-based or radiation-curable inks, especially UV-curable, commercially available, suitably selected for the particular construction of the thermal transfer laminate and / or the particular printing method used. Examples include Sun Sheen (product of Sun Chemical identified as a polyamide ink soluble in alcohol), Suntex MP (product of Sun Chemical identified with a solvent-based ink formulated for the surface printing of substrates coated with acrylic, substrates coated with PVDC and polyolefin films), X-Cel (product of Water Ink Technologies identified as a water-based film ink for printing film substrates), Uvil th AR-109 Rubme Red (product of Daw Ink identified as a UV ink) and CLA9159SF (product of Sun Chemical identified as solvent-based multilink black ink) . The adhesion promoter layers 130 and 135 can be made from any radiation curable, solvent-based or water-based primer designed to increase the adhesion of coatings to a film substrate. The layer 130 is transparent and the layer 135 is preferably transparent. The adhesion promoter layer material is typically composed of a lacquer and a diluent. The lacquer is typically composed of one or more polyolefins, polyamide =, polyesters, polyester copolymers, polyurethanes, polysulfones, polyvinyl chloride, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, ionomers based on sodium or 2 -inc salts or ethylene-methacrylic acid, polyethyl-methacrylates, acrylic polymers and copolymers, polycarbonates, polyacrylonitriles, ethylene-vmyl acetate copolymers, and mixtures of two or more thereof. Examples of the diluents that may be used include ethanol, isopropanol, butanol, ethyl acetate, propyl acetate, butyl acetate, toluene, xylene, acetone, ethyl ethyl ketone, heptane, and mixtures thereof. The ratio of lacquer to diluent depends on the viscosity necessary for the application of the adhesion promoter layer, the selection of such viscosity falling within the knowledge of the subject. Examples of the adhesion promoter layer materials that can be used include CLB04275F - Prokote Primer (product of Sun Chemical Corporation identified as a solvent-based primer that can be used with inks and coatings). Adhesion promoter layers 130 and 135 typically have thicknesses in the range of about 1 to about 4 microns, and in an embodiment of about 2 microns. The transparent abrasion resistant coating layer 140 can be made from any solvent-based, water-based or radiation-curable coating material designed to provide abrasion resistance and optionally better gloss. The coating layer 140 is transparent. Said coating layer is made from UV curable oligomers such as epoxies, urethanes, polyesters, acrylics and the like. These are cured by the free radicals generated by photometers after exposure to UV light. Reactive diluents such as hexanediol diacylate, pentaerythritol, tetraacplate, N-vinyl pyrrolidinone, and the like can be used to control the viscosity of the coating before curing and modifying the crosslinking density. It is also possible to use epoxy and alkyl vinyl ethers, which are cationically cured. Reactive diluents such as vinyl ethers, limonene dioxide, glycidyl ether and the like can be used. The coating may also contain wetting agents, leveling agents, waxes, slip adjuvants and light stabilizers. A commercially available coating material that can be used is RCAQ1302R-UV Coating (product of Sun Chemical identified as a coating material for inks). Said coating layer typically has a thickness of about 1 to about 4 microns, and in an embodiment of about 2 microns. The adhesive layer 150 may consist of any extractable pressure sensitive adhesive material, or radiation curable adhesive material, especially UV curable, suitable for coating a film substrate. When the adhesive layer 150 is a radiation curable adhesive layer, it is transparent. When the adhesive layer 150 is a removable, pressure-sensitive adhesive layer, it is preferably (but not necessarily) transparent. The radiation curable adhesive materials can be made from compositions containing multifunctional acrylate oligomers and monomers. Useful are acrylated urethanes and acrylated acrylics. Radiation curable adhesives may include photoinitiators and optional surfactants to provide a uniform flow that results in a uniform coating. An example of a commercially available adhesive material that can be used is Rad-Cure UV 1008 (product of Rad-Cure Corporation identified as 'solvent-free, UV-curable adhesive, containing 70-95 l' by weight of monomers and oligomers of ulti-functional acrylates, 5-20% by weight of photoinitiator and 0-5% by weight of surfactants.] The removable pressure-sensitive adhesive can be any extractable, pressure-sensitive adhesive known in the art. the material to be used with film substrates The term "extractable" is used herein to refer to an adhesive that can be glued to the layer 140 and the backing sheet 160 without lifting the edge and can be removed without damaging the layer 140 or the sheet 160. The removable adhesive layer 150 preferably adheres to the backing sheet 160 and thus separates the layer 140 from the backing sheet 160. The pressure sensitive adhesives, removable =, which can be used, are known in the art and include rubber-based adhesives, acrylic adhesives, v-ether adhesives, silico-na adhesives, and mixtures of two or more thereof. The adhesives can be hot-melt, solvent-based or water-based adhesives. The pressure-sensitive materials described in "Adhesion and Bond", Encyclopedia of Polymer Science and Engineenng, Vol. 1, pages 476-546, Interscience Publishers, 2 * ed. 198'5, the description of which is incorporated herein by reference. The pressure-sensitive adhesive materials that are useful may contain as the main constituent an adhesive polymer, such as acrylic-type polymers.; block copolymers; natural, regenerated or esti-butadiene rubbers; sticky natural or synthetic rubbers; or random copolymers of ethylene and vinyl acetate, ethylene-vinyl-acrylic terpolymers, polyisotutylene, polyvinyl ether), etc. Other materials may be included in the pressure sensitive adhesive such as tackifying resins, plasticizers, antioxidants, fillers, pigments, waxes, etc. Adhesive layer 150 has a thickness that is typically in the range of about 0.5 to about 5 microns, and in an embodiment of about 1 to about 4 microns, and in an embodiment of about 1.5 to about 2 microns. Each of the layers 120, 130, 140 and 150 is applied and cured using known techniques. Application techniques include engraving, reverse engraving, offset engraving, roll coating, brushing, knife-on-roll, metering roller, reverse roll coating, scraper blade, dipping, die coating, spraying, curtain coating, flexo-graphing, typography, rotary screen, flat screen and analogous. The applied coating layers can be cured by exposure to heat or known forms of ionizing or non-ionizing actinic radiation. The curing temperatures that can be used are of the order of about 40 ° C to about 260 ° C, and in an embodiment of about 40 ° C to about 175 ° C, and in an embodiment of about 40 ° C to about 100 ° C, and in an embodiment from about 40 ° C to about 60 ° C. Useful types of radiation include ultraviolet light, electron beam, x-ray, gamma ray, beta ray, etc. Ultraviolet light is especially useful. The equipment for generating these forms of thermal curing or radiation curing are known to those skilled in the art. The backing sheet 160 is contacted with the adhesive layer 150 by known techniques. When the adhesive 150 is a radiation curable adhesive, the backing sheet 160 is contacted with the adhesive prior to curing the adhesive layer 150. The adhesive layer is then cured. When the adhesive is pressure sensitive adhesive, it can be applied initially to the backing sheet 160 and then the backing sheet is adhered with the adhesive applied to the backing layer 140. Alternatively, the pressure sensitive adhesive can be apply to the coating layer 140, and then the support sheet is contacted with the adhesive to adhere the support sheet to the coating layer 140. The support sheet 160 may be composed of paper, polymeric film, or a combination of them. Any of the paper or polymer films, or combinations thereof, which were previously said to be useful as the layers 112 and 212, can be used as the backing sheet 160. However, it is preferred that the backing sheet 160 be transparent to allow visibility of the ink layer or graphics 120 through the backing sheet 160 (as well as through the other layers between the backing sheet 160 and the ink layer or graphics 120). Thus, the use of transparent polymeric films such as backing sheet 160 is preferred. The outer surface 165 of backing sheet 160 may have a release coating adhered thereto to facilitate coiling and unrolling of thermal transfer laminates. . Any release coating known in the art can be used. Silicone release coatings are especially useful. A commercially available? -liester film that is useful as the backing sheet 160 is Douglas Hanson E19506 (product of Douglas Hanson identified as a clear polyester film with a layer of release coating adhered to one side) . Untreated polyester film can be used. The support sheet 160 typically has a thickness of approximately 0, 0063 to about 0.254 mm (0.25 to 10 mils), and in an embodiment of about 0.0127 to about 0.127 m (0.5 to 5 mils), and in an embodiment of about 0.0508 mm (2 thousandths of a inch). In one embodiment, the backing sheet is a polyester film having a thickness of about 0.0063 to about 0.254 mm (0.25 to 10 m liter). In one embodiment, the backing sheet is a polyolefin film having a thickness of about 0.0127 to about 0.127 mm (0.5 to 5 mils). In one embodiment, the backing sheet is a sheet of paper having a thickness of about 0.0254 to 0.254 mm (1 to 10 mils). The thermal transfer laminates 100, 200 and 200A can be adhered to any substrate using thermal sealing techniques known in the art. Referring to Figure 5, the heat transfer laminate 200A is placed on a substrate 300 with the heat-activatable adhesive layer 230 in contact with the substrate. Heat and pressure are applied to the heat transfer laminate by a hot roll in contact with the support sheet 160. Heat passes through the heat transfer laminate 200A and softens or melts the heat-activatable adhesive layer 230. The heat is removed and the pressure, and the heat-activatable adhesive layer 230 is cooled and solidified resulting in the formation of a heat-sealed bond between the heat transfer laminate 200A and the substrate 300. The heat transfer laminates 100 and 200 can be adhered to the substrate 300 in a similar way, making the heat and pressure that the thermoactivatable adhesive layer 118 or 230 softens or melts, and subsequent cooling of the heat-activatable adhesive layers 118 or 230 results in a heat-sealed bond between the heat transfer laminate 100 or 200 and the substrate 300. The heat and pressure applied are sufficient to soften or melt the heat-sealable adhesive layers 118 or 230. san typically temperatures of the order of about 100 ° C to about 300 ° C, and in an embodiment of about 150 ° C to about 250 ° C, and in an embodiment of about 180 ° C to about 210 ° C. Typically pressures of the order of about 1,406.2 to 14,062 kg / pr (2 to 20 pounds per square inch), and in one embodiment 5,624.8 to 8,437.2 kg / sr (8 to 12 pounds per square inch) are used. ). Residence times of about 0.5 to about 60 seconds can be used, and in an embodiment of about 0.5 to 20 seconds, and in an embodiment of about 0.5 to about 10 seconds. Any heat sealing press used for the labeling of labels, tapes, decals and the like can be used. These are known in the art.

The substrate 300 can be any suitable substrate material for receiving a thermal transfer laminate. The substrate 300 can be made of metal, plastic, leather, paper and the like. The substrate 300 can be made of a textile material such as woven or non-woven fabric made of natural or synthetic materials. The substrate may include an interior surface of the automobile, such as the surface of a safety belt, visor, dashboard, headrest, backrest, door panel, etc. After the application of the thermal transfer laminate to the substrate 300, the support sheet 160 is removed using known extraction or tearing techniques.When the adhesive layer 150 is a removable, pressure sensitive adhesive, it is removed using known techniques. the adhesive layer 150 is a radiation-curable adhesive layer, remains adhered to the coating layer 140 and functions as an additional protective layer This is illustrated in Figure 6. Example 1 Part A A heat transfer laminate is prepared using a film co-extruded polymer as the face block The face block has a central thermoplastic layer, a top thermoplastic film layer having a printable surface with ink adhered to one side of the core layer, and a thermoplastic thermoplastic adhesive film layer adhered On the other side, the thickness of the face block is 0.0889 m (3.5 mils) .The ratio of the thickness of the The thermoplastic thermoplastic adhesive film layer is at 10:60:30. The core layer has the following composition (all percentages by weight): A. Schulman Polybatch PF92D 35% A. Schulman Polybatch White P8555 SD 35% Union Carbide WRD5-1057 23 Ampacet 10561 5? Apipacet 10061 2% The upper thermoplastic film layer has the following composition: Union Carbide WRD5-1057 47% EU 631-04 46% A. Schulman F-20 2% Ampacet 10561 5 $ - "The layer of thermoplastic adhesive film termoactivable has the following composition: Chevron EMAC SP 2268T 83 ?, A. Schulman F20 10% Ampacet 10561 51 Ampacet 10061 2 * The upper thermoplastic film layer is treated in corona, then an adhesion promoter layer is applied on the film layer Superior thermoplastic using an anilox roller The adhesion promoter material is CLB0-4275F - Prokote Primer The adhesion promoter material is cured in an oven at a temperature of 40-50 ° C. This adhesion promoter layer has a thickness A layer of multicolor ink is applied which provides a pictorial design in combination with a printed message on said adhesion promoter layer.The ink layer is applied using a sequence of three rollers ani. The following inks are used: Roller 1: Yellow ink 116 (ink curable by ÜV supplied by Da Ink). Roll 2: Ink to 186 (UV curable ink supplied by Daw Ink). Roller 3: Black ink (UV curable ink supplied by Werneke Ink). Each ink application is UV curved before the next ink application. The ink layer has a thickness of 3 microns. Another adhesion promoter layer is applied on the ink layer using an anilox roll. The pro-adhesion material is CLB04275F - Prokote Primer. Said adhesion promoter layer has a thickness of 2 microns and is cured in an oven at a temperature of 40-50 ° C. A clear abrasion resistant coating layer is applied over the adhesion promoter layer using an anilox roll. The material of the abrasion-resistant coating layer is RCA01302R-UV Coating. The abrasion resistant layer has a thickness of 2 microns and is cured by UV. An adhesive layer is applied over the abrasion resistant coating layer using an anilox roll. The material of the adhesive layer is Rad-Cure UV 1008. The adhesive layer has a thickness of 2 microns. A sheet of polyester film backing with a thickness of 0 is adhered, 0508 mm (2 mils-inch) to the adhesive layer. The adhesive layer is then cured by UV to complete the fabrication of the desired thermal transfer laminate. The polyester film used is supplied by Douglas Hanson under the trade designation E 19506. This is a polyester film having a release coating layer on one of its sides. The side of the polyester film in front of the release coating layer is in contact with the UV cured adhesive layer. Each ink application is cured, as well as the abrasion-resistant clear coating layer, and the UV-curable adhesive layer, using a medium-pressure mercury lamp, an arc length of 45 cm, 500 watts per 2.54 cm (1 inch), a dichromatic reflector and a linear velocity of 19,812 m (65 p is) per i-ñuto. The ink applications and the transparent coating layer are cured using 50o power. The adhesive layer is cured using 100% power. Part B Place the thermal transfer laminate from Part A on a substrate. The substrate is polyester upholstery material with foam reinforcement used for automotive interiors. The thermoactivatable thermoplastic adhesive film layer is in contact with the substrate. The resulting compound is placed in a hot press. Heat and pressure are applied to the composite by a heated roll in contact with the film backing sheet of polyester. The temperature is 196 ° C and the pressure is 6,398.21 kg / ur (9.1 pounds per square inch). The residence time is 2.5 seconds. The heat and pressure are sufficient to soften or melt the heat-activatable thermoplastic adhesive film layer. After cooling, the thermo-sealable thermoplastic adhesive film layer forms a bond that adheres the thermal transfer laminate to the substrate. The compound is removed from the press, the result being that the thermal transfer laminate is heat sealed to the substrate. The polyester film support sheet is removed leaving the remainder of the thermal transfer laminate adhered to the substrate. You can see the multicolored pictorial design formed with the ink layer. The thermal transfer laminates of the invention have several advantages over the prior art. These include the fact that in embodiments where the support sheet 160 is transparent, the ink layer or graphics can be seen during the application of the laminate to a substrate. This feature allows the exact placement of the ink layer or graphics on the substrate. Because of the presence of the face block, the ink or graphics layer applied to the substrate does not conform to minor surface contours or imperfections of the substrate. Thus, the pictorial design and / or the printed message provided by the tmta layer or graphics is clear and precise, and has characteristics of opacity. Once applied to the substrate, the layer of ink or graphics of the laminate of the invention is protected and thus has good characteristics of chemical resistance and is durable. Although the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will be apparent to those skilled in the art after reading the specification. Therefore, it is to be understood that the invention described herein is intended to cover the modifications that fall within the scope of the appended claims.

Claims (25)

1. CLAIMS 1. A thermal transfer laminate, comprising: a face block including a first layer having an upper surface and a lower surface, and a heat-activatable adhesive layer underlying said lower surface of said first layer; an adhesion promoter layer covering said top surface of said first layer; an abrasion-resistant transparent coating layer that overlies said adhesion promoter layer; and another adhesive layer coating said abrasion resistant coating layer.
2. 2. The laminate of claim 1, wherein a backing sheet is adhered to said other adhesive layer.
3. 3. The laminate of claim 1, wherein an ink layer or graphics is placed between said first layer and said adhesion promoter layer.
4. 4. The laminate of claim 1, wherein an ink layer or graphics is placed between said first layer and said adhesion promoter layer, and another adhesion promoter layer is placed between said ink layer or graphs and said first layer. .
5. The laminate of claim 1, wherein said laminate is adhered to a substrate,
6. 6. The laminate of claim 1, wherein said top surface of said first layer is corona treated.
7. 7. The laminate of claim 1, wherein said first layer includes a single layer construction.
8. 8. The laminate of claim 1, wherein said first layer includes a multilayer construction.
9. 9. The laminate of claim 1, wherein said first layer includes sheet metal, paper, polymeric film, textile or a combination thereof.
10. 10. The laminate of claim 1, wherein said first layer comprises a polymeric film.
11. The laminate of claim 1, wherein said first layer consists of a multilayer polymer film.
12. 12. The laminate of claim 1, wherein said face block comprises a coextrudate.
13. The laminate of claim 1, wherein said first layer is a central oplastic layer having an upper surface and a lower surface, and said thermoactivatable adhesive layer is a layer of thermoplastic film underlying said lower surface of said central layer. said face block further comprising a top central thermoplastic layer covering said top surface of said central layer
14. 14. The laminate of claim 13, wherein said top thermoplastic film layer is corona treated.
15. 15. The laminate of claim 13, wherein said upper thermoplastic film layer is composed of a thermoplastic polymer material selected from the group consisting of polyolefms, pol esters, polyamides, acrylic polymers, polystyrenes, polyurethanes, polycarbonates, polyacrylonitrils, copolymers of ethylene-propylene, and mixtures of two or more thereof.
16. 16. The laminate of claim 1, wherein said heat-activatable adhesive layer is composed of a thermoplastic or thermoactivatable adhesive film material selected from the group consisting of polyolefins, polyamides, polyester copolymers, sodium or zinc salt based monomers. of ethylene-methacrylic acid, polyacrylrithyls, ethylene-vinyl acetate copolymers, eti-lenmetacrylic acid, ethylene methyl acrylate, et-nacrylic acid, ethylene ethyl acrylate and mixtures of two or more thereof.
17. 17. The laminate of claim 13, wherein said first layer is composed of a thermoplastic polymer material selected from the group consisting of polyolefins, polyamides, poly esters, polyester copolymers, polyurethanes, polysulfones, styrene-anhydride copolymers. maleic, styrene-acrylonitrile copolymers, ionomers based on sodium or zinc salts of ethylenemethacrylic acid, polymethyl methacrylates, cellulosics, acrylic polymers and copolymers, polycarbonates, polyacrylonitriles, ethylene-villyl acetate copolymers, and mixtures of two or more of them.
18. 18. The laminate of claim 1wherein said adhesion promoter layer is composed of a material selected from the group consisting of pol olefins, polyamides, polyesters, polyester copolymers, polyurethanes, polysulfones, polyvinylidene chloride, styrene-maleic anhydride copolymers, styrene copolymers Acrylonitrile, ionomers based on sodium or zmc salts of ethylenemethacrylic acid, polymethyl ethacrylates, acrylic polymers and epolymers, polycarbonates, polyacrylonitrils, copolymers of ethylene vmyl acetate, and mixtures of two or more thereof.
19. 19. The laminate of claim 1, wherein said transparent abra- sion-resistant coating layer is made of UV-curable oligomers selected from the group consisting of epoxies, urethanes, polyesters and acrylics.
20. 20. The laminate of claim 1, wherein said further adhesive layer is composed of a radiation-curable adhesive material or a removable, pressure-sensitive adhesive material.
21. 21. The laminate of claim 2, wherein said support sheet is composed of paper, polycar- bon film or a combination thereof.
22. 22. The laminate of claim 2, wherein said support sheet is composed of a transparent thermoplastic film.
23. 23. The laminate of claim 5, wherein said substrate is composed of a metal, plastic, leather, paper or textile material, or a combination of two or more thereof.
24. 24. A process for making a thermal transfer laminate, including: arranging a face block including a first layer having an upper surface and a lower surface, and a heat-activatable adhesive layer underlying said lower surface of said first layer; applying an adhesion promoter layer on said top surface of said first layer; curing said adhesion promoter layer; applying a transparent abrasion resistant coating layer on said adhesion promoter layer; and curing said transparent coating layer re- sistant to abrasion; applying another adhesive layer to said layer of abrasion-resistant coating; and adhering a backing sheet to said other adhesive layer.
25. 25. A composite including a substrate and a thermal transfer laminate adhered to said substrate, said thermal transfer laminate including: a face block including a first layer having an upper surface and a lower surface, and a thermoactive adhesive layer that underlies said lower surface of said first layer, said block being adhered facing said substrate by said adhesive layer ter oactivated; an adhesion promoting layer covering said upper surface of said first layer; and an ink layer or graphics coating said adhesion promoter layer; and a transparent abrasion-resistant coating layer that covers said ink layer or graphics.