US20100243140A1 - Thermally Reactive Ink Transfer System - Google Patents
Thermally Reactive Ink Transfer System Download PDFInfo
- Publication number
- US20100243140A1 US20100243140A1 US12/813,870 US81387010A US2010243140A1 US 20100243140 A1 US20100243140 A1 US 20100243140A1 US 81387010 A US81387010 A US 81387010A US 2010243140 A1 US2010243140 A1 US 2010243140A1
- Authority
- US
- United States
- Prior art keywords
- ink
- coating
- decal
- substrate
- transfer system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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Images
Classifications
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- Y10T428/24851—Intermediate layer is discontinuous or differential
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
Definitions
- This invention relates to methods of transferring paint or ink to solid surfaces and more particularly to a method of transferring a substantially solid ink layer to a surface without the use of a separately applied adhesive.
- painted or inked designs are typically applied through application of liquid paint to the surface of a body element, such as a fender or hood.
- An example of this type of application is pinstriping.
- Manual application of stripes or designs requires artistic skill, even if the process is augmented through use of stencils or tape.
- Airbrushed designs are very labor intensive and require considerable skill.
- a decal is created by applying ink to a plastic film bearing adhesive on the opposite surface.
- the adhesive side of the decal may then be applied to the desired surface. Further protection may be achieved by applying a clear, protective, thermoset or photoset coating over the surface to seal the decal against the elements.
- prior art decals have very limited elongation properties and are difficult to apply to highly curved, edged or contoured surfaces. Further problems with prior art decals include separation of the decal from the substrate surface due to failure of the adhesive, and shrinkage, peeling and cracking of the decal itself over time. In addition, the decal typically presents a raised surface that can be felt and observed even after application of a clear coat. The raised decal detracts from the overall appearance and makes the decal prone to increased abrasion, chipping and peeling. Edges of prior on decals are prone to curl after exposure to heat during baking of a thermoset clear coat.
- the present invention presents an ink transfer system including a decal that may be subjected to high temperatures and UV radiation.
- the decal is provided as an alternative to hand painted detail trim for vehicles and accessories such as automobiles, motorcycles, boats, boat motors and helmets.
- the decal may be applied to various metallic, plastic or painted surfaces and is particularly advantageous when applied to pre-painted metal structures that are subjected to baking in order to cure overlying thermoset clear coats.
- An ink transfer system may include one or more layers of temperature and UV resistant ink deposited upon a backing sheet by screening or other currently known or later developed techniques. If a waterslide decal is desired, the ink may be deposited upon waterslide decal paper having a water soluble coating. A transfer medium is deposited over the ink to aid in transfer of the ink to a final receiving substrate. Because the ink is typically deposited upon the backing sheet to form a thin film, the transfer medium aids transfer of the decal from the backing sheet to the substrate without wrinkling or damaging the decal. The transfer medium may be applied over the ink layer through screen printing and it becomes an integral part of the transfer system. Because the transfer medium is designed not to bond to the ink, it is removed prior to application of a subsequent coating such as a clear coat.
- the decal exhibits high flexibility and elongation and may be applied over contoured surfaces. Alternatively, the decal may be applied to a flat surface that is later bent, stamped or otherwise shaped.
- Antioxidants and UV absorbers/light stabilizers are added to the base resin to enhance heat and light stability and to increase tackiness and plasticity of the ink, particularly during heat curing of an overlying clear coat material as is often the case in automotive applications.
- the decal is solid once formed, the ink comprising the decal adheres particularly well to metal and most painted and plastic surfaces due to the low molecular weight polymers comprising the base resin (polymer vehicle).
- the addition of the antioxidants tends to suppress polymerization enhancing the ability of the polymer vehicle to migrate into the adjacent substrate and form a tight bond.
- the decal therefore provides a means for transferring solid ink to a substrate without the need for a separate, intervening adhesive layer.
- the decal When applied to a pre-painted surface, the decal adheres to and binds with the underlying paint to form a uniform coating. Due to the thin layers of ink used to form the decal, the margins of the decal do not noticeably project above the substrate surface and are therefore unlikely to chip or peel, particularly if covered with a clear coating.
- FIG. 1 is a diagrammatical cross sectional view of a decal formed in the manner described herein.
- FIG. 2 is a diagrammatical cross sectional view of a decal formed in the manner described herein.
- FIG. 3 is a top perspective view of a base coat applied to a backing sheet.
- FIG. 4 is a top perspective view of an inked design applied over a portion of the base coat.
- FIG. 5 is a top perspective view of a layer of transfer medium applied to, and extending past the margins of, the inked design and base layer.
- FIG. 6 is a top perspective view of a waterslide decal formed in the manner described herein, the edge of the backing sheet of the decal being positioned against a selected substrate prior to decal transfer.
- FIG. 7 is a top perspective view of the decal of FIG. 6 in which the decal has partially slid off of the backing sheet and onto the substrate surface.
- FIG. 8 is a top perspective view of the decal of FIGS. 6 and 7 in which the decal has been fully removed from the backing sheet and has been oriented in final position upon the substrate.
- FIG. 9 is a top perspective view of the decal of FIGS. 6-8 in which the transfer medium has been partially peeled away from the decal and substrate surfaces.
- FIG. 10 is a top perspective view of the decal of FIGS. 6-9 in which the transfer medium has been fully removed and the decal and substrate are ready for application of a clear over coat.
- FIG. 11 is a top perspective view of the decal of FIGS. 6-10 after application of the clear over coat.
- FIG. 12 is a diagrammatical cross sectional view of a decal formed in the manner described herein.
- An ink transfer system provides for the application of liquid, polyurethane based inks onto a backing sheet to form an ink transfer decal.
- the decal is coated with a removable transfer medium.
- the resultant decal is solidified, typically through evaporation of diluents after application of each layer of liquid constituent. It may then be removed from the backing sheet and applied to a final substrate.
- an ink is provided that upon heating (during baking of a subsequently applied clear coat) becomes plasticized and tacky thereby obviating the need for application or use of a separate adhesive between the decal and the substrate surface. Due to the migration of low molecular weight polymers into the substrate surface, the decal binds to the substrate surface. In the case of pre-painted surfaces, particularly those painted with polyurethane based paints, the decal essentially becomes part of the painted coating.
- a decal comprising thin films of high opacity ink is highly beneficial as it enables rapid application of complex designs to substrate surfaces without the inefficiencies of hand painting while also avoiding problems related to prior art adhesive decals such as peeling from the substrate due to failure of the adhesive; degradation upon subjection to elevated temperatures during baking of an overcoat such as a clear coat or finish; peeling, cracking or curling due to shrinkage; and increased subjection to abrasion or separation from the substrate due to projection of the prior art decal above the substrate surface.
- the ink transfer system of the present invention avoids these disadvantages by providing a thin film decal that self-bonds or adheres to the substrate and does not perceptibly project above the substrate surface. Indeed, upon proper application of the decal and subsequent covering with a clear coat finish, no transition can typically be felt by touch or observed by the naked eye due to location of a decal of the present ink transfer system upon a typical substrate surface.
- FIG. 1 illustrates a diagrammatical cross sectional view of a ink transfer system 100 formed in accordance with the present invention for application of solidified ink to a substrate 101 (see FIGS. 6-11 ), such as a painted automobile, motorcycle or boat body panel or similar surface.
- a substrate 101 such as a painted automobile, motorcycle or boat body panel or similar surface.
- the thickness of the various components are exaggerated in FIGS. 1 and 2 to aid in illustration.
- the ink transfer system 100 includes a backing sheet 102 and transfer medium 104 enclosing transparent base coat 106 and pigmented ink 108 layers, the latter two components comprising the ink transfer decal 109 .
- the transfer medium 104 may also be referred to as a premask.
- the base coat 106 and ink 108 may be referred to herein collectively as ink, inks or ink layers since the base coat 106 is formulated with similar constituents as an ink and may be formulated generally as an unpigmented ink.
- the base coat 106 may comprise a pigmented ink if enhanced opacity is required.
- the primary constituents and formation of the ink transfer system 100 are as follows.
- the backing sheet 102 has an upper surface adapted for receiving solvent-based polymer inks 108 and base coats 106 .
- An appropriate backing sheet 102 is formed of material that will accept the base coat 106 and ink 108 as they are screened upon the sheet 102 without reacting with the inks or softening under the influence of the ink or ink diluents such as organic solvents.
- the upper surface of the backing sheet 102 is typically provided with a thin coating of water soluble material that allows the decal 109 to be later transferred to a substrate 101 using a waterslide technique.
- a base coat 106 is screen printed onto the backing sheet 102 to form an initial layer or coat that helps hold subsequent layers of pigmented ink 108 in proper position to one another. If layers of ink are physically separated from one another, such as with spaced bands 108 a , 108 b and 108 c of pinstriping as shown in FIG. 2 , the base coat 106 provides a means for the individual bands 108 a - 108 c to be joined to one another to form a single ink transfer decal 109 .
- the base layer 106 After the base layer 106 is applied it is dried to evaporate diluents, typically organic solvents. Next, one or more layers of pigmented ink 108 are typically screened onto portions of the base layer 102 . Typically, the pigmented ink 108 is applied so that a portion of the base coat 106 extends beyond the margins of the pigmented ink 108 . If the substrate 101 to which the resulting decal 100 is to be transferred is dark in color, the base coat 106 may contain light-colored (such as white) pigment to provide an opaque, light background to enhance the brightness of overlying layers of colored ink 108 .
- light-colored such as white
- a release coat or layer 110 may be applied to cover and extend beyond the margins of the ink 108 and base 106 layers.
- the release coat 110 may be formulated generally as an upigmented ink 108 .
- a release agent may be added to the release coat 110 formulation to aid in the later separation of the transfer medium 104 from the decal 109 .
- the transfer medium 104 may be applied over the base coat 106 , ink layers 108 and release coat or layer 110 (see FIGS. 1 , 2 and 12 ).
- the transfer medium 104 is typically applied so that it extends beyond the margins of the base layer 106 , ink layer 108 and release coat 110 .
- the transfer medium 104 is typically a clear, flexible coating that protects the decal 109 during storage and greatly aids the dimensional stability of the decal 109 during transfer to a substrate 101 while still allowing sufficient flexion and elongation of the decal 109 for application over, and conformation to, irregularly shaped substrate surfaces.
- the transfer medium 104 may be applied by screen printing, rolling, spraying or other currently known or later developed techniques. A coarser mesh may be used when screen printing the transfer medium 104 in order to deposit a somewhat thicker layer than was deposited when screen printing the base coat 106 and ink layer 108 .
- FIGS. 1 and 2 illustrate the transfer medium 104 applied directly over the ink 108 and base 106 layers.
- FIG. 12 illustrates a release layer 110 disposed between the ink layer 108 and transfer medium 104 . It should be appreciated that FIGS. 1 , 2 and 12 are diagrammatical to show succession of component layers and do not reflect relative dimensions of components, particularly vertical dimensions or thickness.
- the component layers are applied successively as liquids and therefore conform closely to the underlying surfaces.
- voids shown between spaced bands of ink 108 a , 108 b and 108 c would in fact be filled by the transfer medium 104 and the portions of the transfer medium 104 extending beyond the ink 108 and base coat 106 layers would conform to exposed portions of the base coat 106 and backing sheet 102 , respectively.
- the transfer medium 104 is dried to evaporate solvents after which point the ink transfer system 100 has been formed and may be stored until required for transfer of the decal 109 to a substrate 101 .
- the decal 109 and transfer medium 104 may be dried, for example, by passing the system 100 through a wicket cider or by inserting it into a drying rack. Drying for one to two hours is typically optimal but decals 109 may be produced with reduced dry times particularly if the decal 109 is exposed to increased air flow and mild heat such as with a blow dryer held approximately six inches from the decal surface.
- any of the ink or base coat layers 108 and 106 may be transparent, translucent or opaque, however, the base coat 106 is typically transparent unless subsequent coats of ink 108 require an opaque underlying layer to allow the pigment of the ink 108 to more readily show against the color of the substrate.
- a white or otherwise light-colored base coat 106 may be desired so that the coloration of subsequent coats of pigmented ink 108 may be more apparent.
- ink 108 and base coat 106 formulas are selected to provide improvements on the prior art such as heat resistance, chemical resistance, resistance to degradation due to exposure to light (particularly ultraviolet light), high flexibility and elongation characteristics, high tack (particularly during baking after transfer to a substrate) and self-adhesion.
- each table the components are identified.
- the next column provides the percent by weight of each component as a constituent of the example formulation.
- the third column provides approximate percent ranges for each component. These percent ranges do not represent limits for each component but are included as indicative of preferable amounts. Should one or more components be substituted with an equivalent compound it is understood that the relative quantity of the other components may need to be adjusted to optimize the formulation for a particular application or to enhance selected film characteristics. It should be appreciated that evaporation of diluents and/or solvents includes evaporation under ambient conditions as well as through application of heat and/or forced air.
- an initial vehicle (also referred to as a clear varnish) may be prepared as a constituent of the base layer 106 , as well as of the pigmented ink layers 108 , according to the following formulation scheme:
- Vehicle Formulation Component % by weight range Thermoplastic polyester polyurethane based resin 25 20-30 such as resins comprising diphenylmethane diisocyanate.
- Solvent system comprising: Ethyl 3 ethoxypropionate 39 35-45 Cyclohexanone 19 15-25 Diacetone alcohol 17 15-25
- the solvent system is first prepared by mixing the above solvents in an appropriate container.
- the resin is added to the solvents and the contents of the container are heated to the melting point of the resin, typically 100° F. to 140° F.
- the solvents and resin are stirred until the resin has melted and mixed thoroughly with the solvent.
- the sides of the container may be scraped while mixing to insure a homogeneous formulation.
- the formulation of a clear base layer 106 may be prepared according to the following formulation scheme. Note that the base layer 106 formulation may be prepared essentially as unpigmented ink.
- a high molecular weight sterically hindered phenolic antioxidant such as: Irganox 1010 1 0.5-1.5 Irganox 1035 1 0.5-1.5
- Tinuvin 1130, Tinuvin 400, Tinuvin 123, Irganox 1010, and Irganox 1035 are produced by Ciba Specialty Chemicals Corporation.
- a clear base layer 106 may be prepared without UV stabilizers and antioxidants as follows.
- a black pigmented ink may be prepared according to the formula set forth in Table 4.
- the percent of the selected pigment added may be modified as required to obtain the desired color and to increase or decrease opacity of the resultant ink.
- Pigmented Ink Formulation Component % by weight range Vehicle see above
- Vehicle 76.3 50-90 Dibasic ester (solvent) 5 3-8
- Vehicle added as 10 0-10 required up to approximately 10% by weight to optimize viscosity and/or opacity.
- the solvent and pigment may be premixed with a smaller portion of the vehicle, such as 23% by weight, to aid in dispersion and solubilization or suspension of the pigment.
- the premix is transferred for grinding and dispersion of pigment in a three-roll mill. After the premix has been ground in the mill to form a relatively homogeneous dispersion with particulates in the range of 0 to 3 microns, the premix is removed from the mill and mixed with the remaining clear varnish.
- the percentages given for the black pigment are not necessarily representative for other pigment colors.
- white pigment in the range of 30 to 50% of solids.
- a top release coating or layer 110 may be applied over the ink layer 108 .
- a release layer 110 formulation may be formulated according to the formula described in Table 3 for the alternative base layer to comprise 98.5% vehicle and 1.5% flow modifier.
- One or more additional components may be utilized to enhance release of the transfer medium, for example a release layer 110 formulation may comprise 95.55% weight vehicle as described in Table 1, 1.45% weight flow modifier (such as the Modaflow product described above) and 3.0% weight release and flow agent.
- An acceptable release and flow agent includes EFKA-7375 supplied by EFKA Additivies B.V., the Netherlands.
- the release layer 110 may be applied over the ink layer or layers 108 and dried, or allowed to dry, to evaporate the diluent.
- the release layer 110 is typically applied via screen printing and is typically applied to extend beyond the margins of the ink 108 and base 106 layers.
- the release layer 100 increases the overall thickness of the decal 109 and enhances the handleability and dimensional stability of the decal 109 .
- the transfer medium 104 may then be applied over the release layer 110 , the release layer 110 remaining adhered to the ink layer 108 while enhancing release of the transfer medium 104 from the decal.
- the above formulations include a thermoplastic polyester polyurethane as prepared in the vehicle formulation.
- Aliphatic polyurethanes such as polyester polyurethanes are advantageous as they exhibit greater stability in outdoor conditions because they tend to degrade less under exposure to weathering and UV light than aromatic polyurethanes.
- Linear polyurethanes such as those employing 4,4′ diphenylmethane diisocyanate, 4,2′ diphenylmethane diisocyanate and/or 2,2′ diphenylmethane diisocyanate can be formulated to yield a thermoplastic polyester polyurethane with high flexibility and elongation characteristics.
- An appropriate commercial product includes Estane 5715 manufactured by Noveon, Inc.
- UV light can cause degradation and discoloration in ink films. UV light is absorbed by constituent polymers causing bond cleavage and release of free radicals leading to depolymerization. In some cases, excessive crosslinking also occurs causing embrittlement. Therefore, UV stabilizers such as UV absorbers and hindered amine light stabilizers have been added to the disclosed ink and base coat formulations to increase longevity of the decals during exposure to outdoor light and the high intensity UV radiation that may be used to cure photoreactive over-coatings such as clear coats.
- UV stabilizers such as UV absorbers and hindered amine light stabilizers have been added to the disclosed ink and base coat formulations to increase longevity of the decals during exposure to outdoor light and the high intensity UV radiation that may be used to cure photoreactive over-coatings such as clear coats.
- UV absorbers such as substituted hydroxyphenyl-benzotriazoles, hydroxyphenyl-s-triazines, hydroxy-benzophenones and oxalic anilides may be added to the ink and base coat formulations.
- Examples of appropriate commercial products include Tinuvin 1130 and Tinuvin 400 produced by Ciba Specialty Chemicals Corporation.
- HALS hindered amine light stabilizers
- the HALS used with the above exemplary formulations comprises bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)-sebacate.
- Examples of appropriate commercial products include Tinuvin 123 produced by Ciba Specialty Chemicals Corporation.
- Antioxidants such phenolic based anti-oxidants are used to hinder oxidation of ink 108 and base coat 106 polymers and in particular are helpful to hinder thermally induced oxidation during exposure of the decal 109 to elevated temperatures.
- the antioxidants suppress polymerization during curing at ambient temperatures thereby increasing the flexibility and elongation characteristics of the decal 109 as well as essentially eliminating shrinkage and associated problems in the prior art such as peeling and cracking.
- the decal 109 softens due to its thermoplastic qualities and takes on properties of a resinous adhesive.
- the polymerization suppression of the antioxidants causes the ink 108 and base coat films 106 of the decal 109 to become tacky and to bind to one another, the substrate 101 and the clear coat.
- the resultant finish comprises coatings that have substantially fused.
- Suitable phenolic antioxidants include 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propanoic acid, 2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester and benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,thiodi-2,1-ethanediyl ester.
- Suitable commercial antioxidant products for use in ink 108 and base coat 106 formulations include Irganox 1010 and Irganox 1035 produced by Ciba Specialty Chemicals Corporation.
- a flow modifier may be added to the base coat and ink formulations.
- Flow modifiers such Modaflow resin, enhance film properties by aiding in pigment dispersion, facilitating evaporation of solvents and release of entrained air, improving adhesion of the ink film 108 to the substrate 101 or prior ink coatings, including base coat 106 , and reducing surface imperfections of the cured decal films 109 .
- Flow modifiers increase the surface wetting and flow characteristics of the ink as it is screened on to the substrate, enhancing the ink's ability to self level to the substrate surface and enabling the production of thinner decal films 109 .
- Flow modifiers are typically added in the range of 0.1% to 2% of total resin solids but may be adjusted to levels outside of this range to optimize flow characteristics for a given ink formulation.
- a solvent system comprising ethyl 3 ethoxypropionate, cyclohexanone, and diacetone alcohol in the ratio disclosed in Table 1 may be used in formulating the vehicle.
- Dibasic ester may be added to enhance formulation of a pigmented ink.
- Pigments selected to impart color to an ink should be selected for compatibility with other ink components, in particular the polymer resin, and for other advantageous characteristics such as opacity, gloss, bleed resistance and resistance to thermal and light degradation.
- appropriate pigments for use in the disclosed ink formulations include pigments for liquid inks supplied by Sun Chemical Corporation such as red pigment, product No, 228-0013, and violet pigment, product No. 288-0022 which are disclosed in product literature as being heat fast to at least 500′.
- the transfer medium may be prepared according to the following formulation scheme:
- the transfer medium 104 is a film applied in liquid form over the base coat 106 and ink 108 layers. After drying, the transfer medium 104 enhances the handleability of the decal which would otherwise be quite thin and subject to folding over or wrinkling during transfer to the substrate 101 .
- the transfer medium 104 is typically applied to form a thicker film than the individual ink 108 or base coat 106 films.
- the transfer medium 104 disclosed in Table 5 is a film comprised of polyvinyl acetate and nitrocellulose that are formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether, and diacetone alcohol. These solvents are selected to solubilize and compatibilize the nitrocellulose and polyvinyl acetate.
- a flow modifier (such as the Modaflow product described above) is added primarily to enhance surface wetting and flow characteristics of the transfer medium formulation.
- the transfer medium 104 typically does not contain additives to enhance UV or thermal stability because it is removed after application of the decal 109 to the final substrate 101 and discarded.
- Polyvinyl acetate such as polyvinyl acetate beads from McGean, product no. ASB-516, are added to the transfer medium 104 as a binder and for improved adhesion to metal and plastic surfaces.
- Other advantageous characteristics imparted or enhanced by the addition of polyvinyl acetate to the formulation include thermoplasticity, flexibility, solubility in selected solvents, resistance to yellowing, glossiness, transparency, and resistance to oil, grease, and abrasion.
- Nitrocellulose is a film forming polymer and enhances the ability of the transfer medium 104 to become a thin, strong film upon curing.
- polyvinyl acetate enhances the elasticity of the transfer medium film 104
- nitrocellulose enhances the rigidity and strength of the transfer medium film 104 .
- An alternative embodiment of the transfer medium 104 may comprise a release agent for enhanced release and separation of the transfer medium 104 from the ink layer 108 or layers.
- This alternative transfer medium 104 may be prepared according to the following formulation scheme:
- the alternative transfer medium formulation described in Table 6 is comprised of an acrylic methacrylate resin, such as BR-201 (a butyl methacrylate thermoplastic acrylic resin) supplied by Dianal America, Inc., formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether and diacetone alcohol.
- the solvent system is first prepared by transferring specified solvents or equivalents to an appropriate mixing vessel.
- a plasticizer and a release agent may then be added.
- An acceptable commercial plasticizer includes Paraplex G-60 supplied by The C.P. Hall Company.
- An acceptable release agent includes Additol VXL 6383 supplied by Signet Chemical Company.
- the solution is then heated to approximately 140° F. or typically at least to the resin melting point (BR-210 typically melts at temperatures from 110 to 120° F.).
- the resin is then added while mixing the solution and the resulting formulation is stirred until components are in solution and thoroughly mixed.
- a further embodiment of the transfer medium 104 may be prepared according to the following formulation scheme:
- the alternative transfer medium formulation described in Table 7 is comprised of an acrylic methacrylate resin, such as BR-201 (a butyl methacrylate thermoplastic acrylic resin) supplied by Dianal America, Inc., formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether and diacetone alcohol.
- BR-201 a butyl methacrylate thermoplastic acrylic resin
- the solvent system is first prepared by transferring specified solvents or equivalents to an appropriate mixing vessel.
- the release agent such as a silicone-free, fluorocarbon-modified polymer may then be added and the solution mixed.
- the solution is then heated to approximately 140° F. or typically at least to the resin melting point (BR-210 typically melts at temperatures from 110 to 120° F.).
- the resin is then added while mixing the solution, as is the plasticizer.
- the resulting formulation is stirred until components are in solution and thoroughly mixed.
- An acceptable commercial plasticizer includes Paraplex G-60 supplied by The C.P. Hall Company.
- An acceptable release and flow agent includes EFKA-7375 supplied by EFKA Additivies B.V., the Netherlands.
- transfer medium 104 may be prepared by adding 3% by weight of the release agent identified above as Additol VXL 6383 in accordance the following formulation scheme:
- Dispersion of solids in the above formulations may be evaluated using a grind block or smear test. Preferably, mixing is performed until solids are tested as being under approximately 3 microns in size.
- an ink transfer system 100 may be stored until needed.
- the decal 109 may be transferred to a final substrate 101 , such as a pre-painted automotive body part, according to the method or steps set forth below.
- the ink transfer system 100 is trimmed, if desired, to remove excess backing sheet 102 material. Generally, cutting or trimming of the transfer medium 104 should be avoided unless it extends sufficiently beyond the margins of the base coat 106 and ink layers 108 to allow removal of excess.
- the ink transfer system 100 is soaked in water for several minutes, two or more minutes generally sufficing for relatively small decals. Extended periods of soaking should be avoided as the water soluble coating on the backing sheet 102 may dissolve sufficiently to cause the decal 109 and transfer medium 104 layers to fall away from the backing sheet 102 .
- FIG. 6 is a top perspective view of the lower edge of the backing sheet 102 positioned against a final substrate 101 with the ink transfer system 100 facing the viewer.
- the decal 109 including the attached transfer medium 104 is then slid off of the backing sheet 102 .
- FIG. 7 the decal 109 has been slid partially off of the backing sheet 102 and onto the surface of the substrate 101 .
- the decal 109 is held together by the strong adhesion of the base coat 106 , ink layers 108 , and release coat 110 to one another and the weaker, though sufficient, adhesion of the transfer medium 104 to the release coat 110 .
- the transfer medium 104 is not composed of the same material as the ink 108 and, although flexible and capable of stretching, it is less so than the release coat 110 , ink 108 and base coat 106 layers since it is designed to provide dimensional stability during transfer of the decal 109 .
- the transfer medium 104 is also typically screen printed or otherwise deposited to form a somewhat thicker layer.
- the ink transfer decal 109 is applied to the substrate surface 101 with the transfer medium 104 on top and the base coat 106 contacting the substrate surface 101 . Due to the moisture on the decal 109 (the substrate may also be prewetted, for example by spraying with water from a spray bottle or hose, not shown) and the thinness and flexibility of the decal 109 , the surface tension of the water between the decal 109 and the substrate 101 causes the decal 109 to conform closely to the substrate surface 101 and to loosely adhere. At this point the decal 109 may be moved or adjusted to its final position, often determined by registration marks (not shown) on the substrate 101 , and any wrinkles or bubbles may be smoothed out using a squeegee, sponge or other appropriate device.
- the decal 109 is shown fully removed from the backing sheet 102 and placed in final position upon the substrate surface 101 .
- the dashed lines defining the ink 108 and base coat 106 layers indicate that these layers are covered by and viewed through the transfer medium 104 .
- the ink 108 and base coats 106 are prepared from linear chain polyester polyurethanes, and polymerization is somewhat suppressed through use of antioxidants, the ink 108 and base coat 106 films of the decal 109 are extremely flexible and exhibit high elongation characteristics. Elongation of over 400% may be obtained when stretching the ink 108 and base coats 106 . Because of these properties, the decal 109 may be applied to molded surfaces having irregular shapes.
- the transfer medium 104 allows for stretching and other manipulation of the decal 109 during application to the substrate 101 while aiding in handling of the decal 109 which would otherwise be difficult due to the extreme thinness of the ink 108 and base coat 106 layers. In other applications, the decal 109 may be transferred to a relatively flat surface for ease of registering and then subjected to considerable stretching and elongation due to bending or stamping of the piece post-transfer.
- the decal 109 is then allowed to dry through air drying or other means. After the decal 109 and transfer medium 104 dries and substantially all surface moisture has evaporated, typically 1 to 24 hours after transfer, the transfer medium 104 may be peeled away from the deposited decal 109 .
- FIG. 9 provides a top perspective view of the decal 109 showing a portion of the transfer medium 104 peeled away from the decal 109 and substrate 101 . Because it is removed after the water between the decal 109 and the substrate 101 has evaporated, it is important that the transfer layer 104 not stick or bind to the decal 109 excessively.
- FIG. 10 illustrates the decal 109 after removal of the transfer medium 104 . At this point in the transfer process a clear base coat 106 may still be slightly visible or discernable from the surrounding surface of the substrate 101 .
- a clear coat may be applied.
- a commonly used, solvent-based, thermoset clear coat is typically applied by spraying.
- Such clear coatings often comprise thermoset polyurethanes that must go through a heat conversion to complete polymerization. Because of the extensive polymerization and crosslinking such coatings typically provide very good chemical resistance.
- a photoreactive (UV) coating may be applied.
- FIG. 11 is a top perspective view of the decal 109 after application of the clear coat and baking.
- the decal 109 has fused to the substrate 101 and clear coat and, due to the thinness of the base coat 106 and ink 108 layers, presents a design that does not protrude or project above the adjacent finish.
- the substrate 101 bearing the decal 109 and overlying clear coat is then baked in an oven or otherwise heated to temperatures typically in the range of 250 to 325 degrees Fahrenheit. Due to the presence of antioxidants, the ink 108 and base coat 106 films may readily withstand exposure to such temperatures without degradation, discoloration, shrinkage, peeling or other defects.
- the decal 109 softens becoming fluid or semi-fluid. While heated the decal 109 further polymerizes and adheres to compatible underlying surfaces such as typical polyurethane-based paints and coatings used in the automotive industry.
- the softening and adherence characteristics of the decal 109 are typically achieved as the temperature during the baking cycle rises to 185° F. and continue to improve as the temperature increases to 265° F.
- the decal 109 may be subjected to temperatures in excess of 375° F.
- the ink film forming mechanism employed in the above ink embodiments is partially that of a solvent evaporative coating yielding a thermoplastic ink film. Film formation occurs during evaporation of the diluents and the concomitant coalescence of the polymer chains. Polymerization to form linear, polyester-based polyurethane chains yields an ink film having thermoplastic characteristics while still exhibiting good resistance to solvents and other chemicals after curing.
- free isocyanates may be added to the ink formulation.
- Free isocyanates with particular advantages include aliphatic polyisocyanate resins based on hexamethylene diisocyanate. Such compounds react well with polyester hydroxyl-functional coreactants such as are used to prepare the vehicle described in Table 1. Resultant coatings prepared using polyisocyanate compounds exhibit enhanced resistance to solvents and oxidizing chemicals as well as increased abrasion resistance. The coatings have enhanced light stability, resistance to heat degradation and resist yellowing or other discoloration.
- a commercial product appropriate for providing free isocyanates with the above advantages includes Desmodur N 100, produced by Bayer Polymers LLC. Typically, these products are added to the ink formulation at levels of 0.005 to 0.01% of resin solids.
- a thermal set ink transfer system may be provided through the addition to the ink 108 and base coat 106 formulations of melamine and an acid catalyst.
- the melamine reacts with the acid catalyst to form crosslinkages that set the film, reducing or eliminating thermoplasticity but increasing chemical and heat resistance.
Landscapes
- Decoration By Transfer Pictures (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
An ink transfer system including an ink transfer decal that is transferable to a final substrate, such as a bare metal or pre-painted autobody part, without use of a separate adhesive. The transferred ink decal is capable of withstanding temperature elevations common during automotive paint baking without significant thermal degradation, discoloration, shrinkage or pealing.
Description
- This invention relates to methods of transferring paint or ink to solid surfaces and more particularly to a method of transferring a substantially solid ink layer to a surface without the use of a separately applied adhesive.
- In the vehicle manufacturing industry, painted or inked designs are typically applied through application of liquid paint to the surface of a body element, such as a fender or hood. An example of this type of application is pinstriping. Manual application of stripes or designs requires artistic skill, even if the process is augmented through use of stencils or tape. Airbrushed designs are very labor intensive and require considerable skill.
- One prior art method of automating the application of designs or stripes is the use of adhesive decals. A decal is created by applying ink to a plastic film bearing adhesive on the opposite surface. The adhesive side of the decal may then be applied to the desired surface. Further protection may be achieved by applying a clear, protective, thermoset or photoset coating over the surface to seal the decal against the elements.
- These prior art decals have very limited elongation properties and are difficult to apply to highly curved, edged or contoured surfaces. Further problems with prior art decals include separation of the decal from the substrate surface due to failure of the adhesive, and shrinkage, peeling and cracking of the decal itself over time. In addition, the decal typically presents a raised surface that can be felt and observed even after application of a clear coat. The raised decal detracts from the overall appearance and makes the decal prone to increased abrasion, chipping and peeling. Edges of prior on decals are prone to curl after exposure to heat during baking of a thermoset clear coat.
- The present invention presents an ink transfer system including a decal that may be subjected to high temperatures and UV radiation. The decal is provided as an alternative to hand painted detail trim for vehicles and accessories such as automobiles, motorcycles, boats, boat motors and helmets. The decal may be applied to various metallic, plastic or painted surfaces and is particularly advantageous when applied to pre-painted metal structures that are subjected to baking in order to cure overlying thermoset clear coats.
- An ink transfer system according to the present invention may include one or more layers of temperature and UV resistant ink deposited upon a backing sheet by screening or other currently known or later developed techniques. If a waterslide decal is desired, the ink may be deposited upon waterslide decal paper having a water soluble coating. A transfer medium is deposited over the ink to aid in transfer of the ink to a final receiving substrate. Because the ink is typically deposited upon the backing sheet to form a thin film, the transfer medium aids transfer of the decal from the backing sheet to the substrate without wrinkling or damaging the decal. The transfer medium may be applied over the ink layer through screen printing and it becomes an integral part of the transfer system. Because the transfer medium is designed not to bond to the ink, it is removed prior to application of a subsequent coating such as a clear coat.
- The decal exhibits high flexibility and elongation and may be applied over contoured surfaces. Alternatively, the decal may be applied to a flat surface that is later bent, stamped or otherwise shaped.
- Antioxidants and UV absorbers/light stabilizers are added to the base resin to enhance heat and light stability and to increase tackiness and plasticity of the ink, particularly during heat curing of an overlying clear coat material as is often the case in automotive applications. Although the decal is solid once formed, the ink comprising the decal adheres particularly well to metal and most painted and plastic surfaces due to the low molecular weight polymers comprising the base resin (polymer vehicle). The addition of the antioxidants tends to suppress polymerization enhancing the ability of the polymer vehicle to migrate into the adjacent substrate and form a tight bond. The decal therefore provides a means for transferring solid ink to a substrate without the need for a separate, intervening adhesive layer. When applied to a pre-painted surface, the decal adheres to and binds with the underlying paint to form a uniform coating. Due to the thin layers of ink used to form the decal, the margins of the decal do not noticeably project above the substrate surface and are therefore unlikely to chip or peel, particularly if covered with a clear coating.
- Other advantages of the invention will become apparent from the following description taken in connection with the accompanying drawings, wherein is set forth by way of illustration and example, embodiments of the present invention.
-
FIG. 1 is a diagrammatical cross sectional view of a decal formed in the manner described herein. -
FIG. 2 is a diagrammatical cross sectional view of a decal formed in the manner described herein. -
FIG. 3 . is a top perspective view of a base coat applied to a backing sheet. -
FIG. 4 is a top perspective view of an inked design applied over a portion of the base coat. -
FIG. 5 is a top perspective view of a layer of transfer medium applied to, and extending past the margins of, the inked design and base layer. -
FIG. 6 is a top perspective view of a waterslide decal formed in the manner described herein, the edge of the backing sheet of the decal being positioned against a selected substrate prior to decal transfer. -
FIG. 7 is a top perspective view of the decal ofFIG. 6 in which the decal has partially slid off of the backing sheet and onto the substrate surface. -
FIG. 8 is a top perspective view of the decal ofFIGS. 6 and 7 in which the decal has been fully removed from the backing sheet and has been oriented in final position upon the substrate. -
FIG. 9 is a top perspective view of the decal ofFIGS. 6-8 in which the transfer medium has been partially peeled away from the decal and substrate surfaces. -
FIG. 10 is a top perspective view of the decal ofFIGS. 6-9 in which the transfer medium has been fully removed and the decal and substrate are ready for application of a clear over coat. -
FIG. 11 is a top perspective view of the decal ofFIGS. 6-10 after application of the clear over coat. -
FIG. 12 is a diagrammatical cross sectional view of a decal formed in the manner described herein. - As required, a detailed embodiment of the present invention is disclosed herein; however, it is to be understood that the disclosed embodiment is merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure.
- An ink transfer system according to the present invention provides for the application of liquid, polyurethane based inks onto a backing sheet to form an ink transfer decal. The decal is coated with a removable transfer medium. The resultant decal is solidified, typically through evaporation of diluents after application of each layer of liquid constituent. It may then be removed from the backing sheet and applied to a final substrate.
- Through the use of low molecular weight aliphatic polymers and antioxidants for polymerization suppression, an ink is provided that upon heating (during baking of a subsequently applied clear coat) becomes plasticized and tacky thereby obviating the need for application or use of a separate adhesive between the decal and the substrate surface. Due to the migration of low molecular weight polymers into the substrate surface, the decal binds to the substrate surface. In the case of pre-painted surfaces, particularly those painted with polyurethane based paints, the decal essentially becomes part of the painted coating.
- The provision of a decal comprising thin films of high opacity ink is highly beneficial as it enables rapid application of complex designs to substrate surfaces without the inefficiencies of hand painting while also avoiding problems related to prior art adhesive decals such as peeling from the substrate due to failure of the adhesive; degradation upon subjection to elevated temperatures during baking of an overcoat such as a clear coat or finish; peeling, cracking or curling due to shrinkage; and increased subjection to abrasion or separation from the substrate due to projection of the prior art decal above the substrate surface. The ink transfer system of the present invention avoids these disadvantages by providing a thin film decal that self-bonds or adheres to the substrate and does not perceptibly project above the substrate surface. Indeed, upon proper application of the decal and subsequent covering with a clear coat finish, no transition can typically be felt by touch or observed by the naked eye due to location of a decal of the present ink transfer system upon a typical substrate surface.
- Referring now to the drawings,
FIG. 1 illustrates a diagrammatical cross sectional view of aink transfer system 100 formed in accordance with the present invention for application of solidified ink to a substrate 101 (seeFIGS. 6-11 ), such as a painted automobile, motorcycle or boat body panel or similar surface. The thickness of the various components are exaggerated inFIGS. 1 and 2 to aid in illustration. - The
ink transfer system 100 includes abacking sheet 102 andtransfer medium 104 enclosingtransparent base coat 106 and pigmentedink 108 layers, the latter two components comprising theink transfer decal 109. Thetransfer medium 104 may also be referred to as a premask. Thebase coat 106 andink 108 may be referred to herein collectively as ink, inks or ink layers since thebase coat 106 is formulated with similar constituents as an ink and may be formulated generally as an unpigmented ink. In addition, thebase coat 106 may comprise a pigmented ink if enhanced opacity is required. The primary constituents and formation of theink transfer system 100 are as follows. Thebacking sheet 102 has an upper surface adapted for receiving solvent-basedpolymer inks 108 and base coats 106. Anappropriate backing sheet 102 is formed of material that will accept thebase coat 106 andink 108 as they are screened upon thesheet 102 without reacting with the inks or softening under the influence of the ink or ink diluents such as organic solvents. The upper surface of thebacking sheet 102 is typically provided with a thin coating of water soluble material that allows thedecal 109 to be later transferred to asubstrate 101 using a waterslide technique. - Typically, although not necessarily, a
base coat 106 is screen printed onto thebacking sheet 102 to form an initial layer or coat that helps hold subsequent layers of pigmentedink 108 in proper position to one another. If layers of ink are physically separated from one another, such as with spacedbands FIG. 2 , thebase coat 106 provides a means for theindividual bands 108 a-108 c to be joined to one another to form a singleink transfer decal 109. - After the
base layer 106 is applied it is dried to evaporate diluents, typically organic solvents. Next, one or more layers of pigmentedink 108 are typically screened onto portions of thebase layer 102. Typically, the pigmentedink 108 is applied so that a portion of thebase coat 106 extends beyond the margins of the pigmentedink 108. If thesubstrate 101 to which the resultingdecal 100 is to be transferred is dark in color, thebase coat 106 may contain light-colored (such as white) pigment to provide an opaque, light background to enhance the brightness of overlying layers ofcolored ink 108. - After solvents or diluents have substantially evaporated from the ink layer or layers 108, a release coat or
layer 110 may be applied to cover and extend beyond the margins of theink 108 and base 106 layers. As with thebase coat 106, therelease coat 110 may be formulated generally as anupigmented ink 108. In addition, a release agent may be added to therelease coat 110 formulation to aid in the later separation of the transfer medium 104 from thedecal 109. - After solvents or diluents have substantially evaporated from each previous layer or coat, the
transfer medium 104 may be applied over thebase coat 106, ink layers 108 and release coat or layer 110 (seeFIGS. 1 , 2 and 12). Thetransfer medium 104 is typically applied so that it extends beyond the margins of thebase layer 106,ink layer 108 andrelease coat 110. Thetransfer medium 104 is typically a clear, flexible coating that protects thedecal 109 during storage and greatly aids the dimensional stability of thedecal 109 during transfer to asubstrate 101 while still allowing sufficient flexion and elongation of thedecal 109 for application over, and conformation to, irregularly shaped substrate surfaces. As with the previously appliedink 108,base 106 and release 110 layers, thetransfer medium 104 may be applied by screen printing, rolling, spraying or other currently known or later developed techniques. A coarser mesh may be used when screen printing thetransfer medium 104 in order to deposit a somewhat thicker layer than was deposited when screen printing thebase coat 106 andink layer 108.FIGS. 1 and 2 illustrate thetransfer medium 104 applied directly over theink 108 and base 106 layers.FIG. 12 illustrates arelease layer 110 disposed between theink layer 108 andtransfer medium 104. It should be appreciated thatFIGS. 1 , 2 and 12 are diagrammatical to show succession of component layers and do not reflect relative dimensions of components, particularly vertical dimensions or thickness. In addition, it should be appreciated that the component layers are applied successively as liquids and therefore conform closely to the underlying surfaces. For example, voids shown between spaced bands ofink transfer medium 104 and the portions of thetransfer medium 104 extending beyond theink 108 andbase coat 106 layers would conform to exposed portions of thebase coat 106 andbacking sheet 102, respectively. - After screen printing, the
transfer medium 104 is dried to evaporate solvents after which point theink transfer system 100 has been formed and may be stored until required for transfer of thedecal 109 to asubstrate 101. At each stage of solvent evaporation discussed above, thedecal 109 andtransfer medium 104 may be dried, for example, by passing thesystem 100 through a wicket cider or by inserting it into a drying rack. Drying for one to two hours is typically optimal butdecals 109 may be produced with reduced dry times particularly if thedecal 109 is exposed to increased air flow and mild heat such as with a blow dryer held approximately six inches from the decal surface. - Any of the ink or base coat layers 108 and 106 may be transparent, translucent or opaque, however, the
base coat 106 is typically transparent unless subsequent coats ofink 108 require an opaque underlying layer to allow the pigment of theink 108 to more readily show against the color of the substrate. For example, if thedecal 109 is to be transferred to a dark colored substrate, a white or otherwise light-colored base coat 106 may be desired so that the coloration of subsequent coats of pigmentedink 108 may be more apparent. - The following examples are provided to further disclose the invention. In these examples as well as throughout the specification and in the claims, unless otherwise indicated, all parts and percentages are by weight. The constituents of the
ink 108 andbase coat 106 formulas are selected to provide improvements on the prior art such as heat resistance, chemical resistance, resistance to degradation due to exposure to light (particularly ultraviolet light), high flexibility and elongation characteristics, high tack (particularly during baking after transfer to a substrate) and self-adhesion. - In the first column in each table the components are identified. The next column provides the percent by weight of each component as a constituent of the example formulation. The third column provides approximate percent ranges for each component. These percent ranges do not represent limits for each component but are included as indicative of preferable amounts. Should one or more components be substituted with an equivalent compound it is understood that the relative quantity of the other components may need to be adjusted to optimize the formulation for a particular application or to enhance selected film characteristics. It should be appreciated that evaporation of diluents and/or solvents includes evaporation under ambient conditions as well as through application of heat and/or forced air.
- By way of example, an initial vehicle (also referred to as a clear varnish) may be prepared as a constituent of the
base layer 106, as well as of the pigmented ink layers 108, according to the following formulation scheme: -
TABLE 1 Vehicle Formulation Component % by weight range Thermoplastic polyester polyurethane based resin 25 20-30 such as resins comprising diphenylmethane diisocyanate. Solvent system comprising: Ethyl 3 ethoxypropionate 39 35-45 Cyclohexanone 19 15-25 Diacetone alcohol 17 15-25 - To prepare the vehicle, the solvent system is first prepared by mixing the above solvents in an appropriate container. The resin is added to the solvents and the contents of the container are heated to the melting point of the resin, typically 100° F. to 140° F. The solvents and resin are stirred until the resin has melted and mixed thoroughly with the solvent. The sides of the container may be scraped while mixing to insure a homogeneous formulation.
- The formulation of a
clear base layer 106 may be prepared according to the following formulation scheme. Note that thebase layer 106 formulation may be prepared essentially as unpigmented ink. -
TABLE 2 Base Layer Formulation Component % by weight range Vehicle (see above) 92 85-95 Resin flow modifier such as Modaflow produced 2 1.5-2.5 by Solutia Inc. UV absorbers such as substituted hydroxyphenyl- 3 1-4 benzotriazoles, hydroxyphenyl-s-triazines, hydroxy-benzophenones and oxalic anilides, for example Tinuvin 1130 or Tinuvin 400. Hindered amine light stabilizers such as those 1 0.5-1.5 derived from 2,2,6,6-tetraalkyl piperidine, substituted piperizinedione, and/or decanedioic acid, for example Tinuvin 123. A high molecular weight sterically hindered phenolic antioxidant such as: Irganox 1010 1 0.5-1.5 Irganox 1035 1 0.5-1.5 Note: Tinuvin 1130, Tinuvin 400, Tinuvin 123, Irganox 1010, and Irganox 1035 are produced by Ciba Specialty Chemicals Corporation. - Alternatively, a
clear base layer 106 may be prepared without UV stabilizers and antioxidants as follows. -
TABLE 3 Alternative Base Layer Formulation Component % by weight range Vehicle (see above) 98.5 97.5-100 Resin flow modifier 1.5 1.0-2.5 - As an example of a pigmented
ink 108, a black pigmented ink may be prepared according to the formula set forth in Table 4. For other colors, the percent of the selected pigment added may be modified as required to obtain the desired color and to increase or decrease opacity of the resultant ink. -
TABLE 4 Pigmented Ink Formulation Component % by weight range Vehicle (see above) 76.3 50-90 Dibasic ester (solvent) 5 3-8 Black pigment 7.2 5-8 Resin flow modifier 1.5 1.5-2.5 Vehicle (see above) added as 10 0-10 required up to approximately 10% by weight to optimize viscosity and/or opacity.
The solvent and pigment may be premixed with a smaller portion of the vehicle, such as 23% by weight, to aid in dispersion and solubilization or suspension of the pigment. Typically, the premix is transferred for grinding and dispersion of pigment in a three-roll mill. After the premix has been ground in the mill to form a relatively homogeneous dispersion with particulates in the range of 0 to 3 microns, the premix is removed from the mill and mixed with the remaining clear varnish. - The percentages given for the black pigment are not necessarily representative for other pigment colors. For example, when preparing a white Mk it may be advantageous to add white pigment in the range of 30 to 50% of solids.
- A top release coating or
layer 110 may be applied over theink layer 108. Arelease layer 110 formulation may be formulated according to the formula described in Table 3 for the alternative base layer to comprise 98.5% vehicle and 1.5% flow modifier. One or more additional components may be utilized to enhance release of the transfer medium, for example arelease layer 110 formulation may comprise 95.55% weight vehicle as described in Table 1, 1.45% weight flow modifier (such as the Modaflow product described above) and 3.0% weight release and flow agent. An acceptable release and flow agent includes EFKA-7375 supplied by EFKA Additivies B.V., the Netherlands. - Once formulated, the
release layer 110 may be applied over the ink layer or layers 108 and dried, or allowed to dry, to evaporate the diluent. Therelease layer 110 is typically applied via screen printing and is typically applied to extend beyond the margins of theink 108 and base 106 layers. Therelease layer 100 increases the overall thickness of thedecal 109 and enhances the handleability and dimensional stability of thedecal 109. Thetransfer medium 104 may then be applied over therelease layer 110, therelease layer 110 remaining adhered to theink layer 108 while enhancing release of the transfer medium 104 from the decal. - The above formulations include a thermoplastic polyester polyurethane as prepared in the vehicle formulation. Aliphatic polyurethanes such as polyester polyurethanes are advantageous as they exhibit greater stability in outdoor conditions because they tend to degrade less under exposure to weathering and UV light than aromatic polyurethanes. Linear polyurethanes such as those employing 4,4′ diphenylmethane diisocyanate, 4,2′ diphenylmethane diisocyanate and/or 2,2′ diphenylmethane diisocyanate can be formulated to yield a thermoplastic polyester polyurethane with high flexibility and elongation characteristics. An appropriate commercial product includes Estane 5715 manufactured by Noveon, Inc.
- UV light can cause degradation and discoloration in ink films. UV light is absorbed by constituent polymers causing bond cleavage and release of free radicals leading to depolymerization. In some cases, excessive crosslinking also occurs causing embrittlement. Therefore, UV stabilizers such as UV absorbers and hindered amine light stabilizers have been added to the disclosed ink and base coat formulations to increase longevity of the decals during exposure to outdoor light and the high intensity UV radiation that may be used to cure photoreactive over-coatings such as clear coats. UV absorbers such as substituted hydroxyphenyl-benzotriazoles, hydroxyphenyl-s-triazines, hydroxy-benzophenones and oxalic anilides may be added to the ink and base coat formulations. Examples of appropriate commercial products include Tinuvin 1130 and Tinuvin 400 produced by Ciba Specialty Chemicals Corporation.
- Further protection from degradation due to UV radiation may be obtained through the addition of hindered amine light stabilizers (HALS) such as those derived from 2,2,6,6-tetraalkyl piperidine, substituted piperizinedione, and/or decanedioic acid. The HALS used with the above exemplary formulations comprises bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)-sebacate. Examples of appropriate commercial products include Tinuvin 123 produced by Ciba Specialty Chemicals Corporation.
- Antioxidants such phenolic based anti-oxidants are used to hinder oxidation of
ink 108 andbase coat 106 polymers and in particular are helpful to hinder thermally induced oxidation during exposure of thedecal 109 to elevated temperatures. In addition to protecting thedecal 109 during exposure to heat, the antioxidants suppress polymerization during curing at ambient temperatures thereby increasing the flexibility and elongation characteristics of thedecal 109 as well as essentially eliminating shrinkage and associated problems in the prior art such as peeling and cracking. During baking of the substrate material, after transfer of thedecal 109 and application of the clear over coat, thedecal 109 softens due to its thermoplastic qualities and takes on properties of a resinous adhesive. At this time, the polymerization suppression of the antioxidants causes theink 108 andbase coat films 106 of thedecal 109 to become tacky and to bind to one another, thesubstrate 101 and the clear coat. Once baking of the clear coat is completed and thesubstrate 101 is allowed to cool to ambient temperatures, the resultant finish comprises coatings that have substantially fused. Suitable phenolic antioxidants include 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propanoic acid, 2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propanediyl ester and benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,thiodi-2,1-ethanediyl ester. Suitable commercial antioxidant products for use inink 108 andbase coat 106 formulations include Irganox 1010 and Irganox 1035 produced by Ciba Specialty Chemicals Corporation. - As indicated above, a flow modifier may be added to the base coat and ink formulations. Flow modifiers, such Modaflow resin, enhance film properties by aiding in pigment dispersion, facilitating evaporation of solvents and release of entrained air, improving adhesion of the
ink film 108 to thesubstrate 101 or prior ink coatings, includingbase coat 106, and reducing surface imperfections of the cureddecal films 109. - Flow modifiers increase the surface wetting and flow characteristics of the ink as it is screened on to the substrate, enhancing the ink's ability to self level to the substrate surface and enabling the production of
thinner decal films 109. Flow modifiers are typically added in the range of 0.1% to 2% of total resin solids but may be adjusted to levels outside of this range to optimize flow characteristics for a given ink formulation. - A solvent system comprising ethyl 3 ethoxypropionate, cyclohexanone, and diacetone alcohol in the ratio disclosed in Table 1 may be used in formulating the vehicle. Dibasic ester may be added to enhance formulation of a pigmented ink.
- Pigments selected to impart color to an ink should be selected for compatibility with other ink components, in particular the polymer resin, and for other advantageous characteristics such as opacity, gloss, bleed resistance and resistance to thermal and light degradation. Examples of appropriate pigments for use in the disclosed ink formulations include pigments for liquid inks supplied by Sun Chemical Corporation such as red pigment, product No, 228-0013, and violet pigment, product No. 288-0022 which are disclosed in product literature as being heat fast to at least 500′.
- The transfer medium may be prepared according to the following formulation scheme:
-
TABLE 5 Transfer Medium Formulation Component % by weight range Propylene glycol methyl ether acetate (solvent) 40 25-50 Propylene glycol methyl ether (solvent) 17 10-25 Diacetone alcohol 10 5-15 Resin flow modifier 3 1-6 Nitrocellulose 10 5-15 Polyvinyl acetate resin 20 10-30 - The
transfer medium 104 is a film applied in liquid form over thebase coat 106 andink 108 layers. After drying, thetransfer medium 104 enhances the handleability of the decal which would otherwise be quite thin and subject to folding over or wrinkling during transfer to thesubstrate 101. Thetransfer medium 104 is typically applied to form a thicker film than theindividual ink 108 orbase coat 106 films. Thetransfer medium 104 disclosed in Table 5 is a film comprised of polyvinyl acetate and nitrocellulose that are formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether, and diacetone alcohol. These solvents are selected to solubilize and compatibilize the nitrocellulose and polyvinyl acetate. A flow modifier (such as the Modaflow product described above) is added primarily to enhance surface wetting and flow characteristics of the transfer medium formulation. Thetransfer medium 104 typically does not contain additives to enhance UV or thermal stability because it is removed after application of thedecal 109 to thefinal substrate 101 and discarded. - Polyvinyl acetate, such as polyvinyl acetate beads from McGean, product no. ASB-516, are added to the
transfer medium 104 as a binder and for improved adhesion to metal and plastic surfaces. Other advantageous characteristics imparted or enhanced by the addition of polyvinyl acetate to the formulation include thermoplasticity, flexibility, solubility in selected solvents, resistance to yellowing, glossiness, transparency, and resistance to oil, grease, and abrasion. - Nitrocellulose is a film forming polymer and enhances the ability of the
transfer medium 104 to become a thin, strong film upon curing. In general, polyvinyl acetate enhances the elasticity of thetransfer medium film 104, while nitrocellulose enhances the rigidity and strength of thetransfer medium film 104. - An alternative embodiment of the
transfer medium 104 may comprise a release agent for enhanced release and separation of the transfer medium 104 from theink layer 108 or layers. Thisalternative transfer medium 104 may be prepared according to the following formulation scheme: -
TABLE 6 Alternative Transfer Medium Formulation Component % by weight range Acrylic methacrylate resin 34.8 25-40 Plasticizer 10 7-12 Release agent 3 1-5 Solvent system comprising: Propylene glycol methyl ether acetate 33 25-35 Propylene glycol methyl ether 12.2 10-15 Diacetone alcohol 7 5-10 - The alternative transfer medium formulation described in Table 6 is comprised of an acrylic methacrylate resin, such as BR-201 (a butyl methacrylate thermoplastic acrylic resin) supplied by Dianal America, Inc., formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether and diacetone alcohol. Typically, the solvent system is first prepared by transferring specified solvents or equivalents to an appropriate mixing vessel. A plasticizer and a release agent may then be added. An acceptable commercial plasticizer includes Paraplex G-60 supplied by The C.P. Hall Company. An acceptable release agent includes Additol VXL 6383 supplied by Signet Chemical Company. The solution is then heated to approximately 140° F. or typically at least to the resin melting point (BR-210 typically melts at temperatures from 110 to 120° F.). The resin is then added while mixing the solution and the resulting formulation is stirred until components are in solution and thoroughly mixed.
- A further embodiment of the
transfer medium 104 may be prepared according to the following formulation scheme: -
TABLE 7 Alternative Transfer Medium Formulation Component % by weight range Acrylic methacrylate resin 28.48 Plasticizer 8 Release agent 3 Solvent system comprising: Propylene glycol methyl ether acetate 37.38 Propylene glycol methyl ether 14.24 Diacetone alcohol 8.9 - The alternative transfer medium formulation described in Table 7 is comprised of an acrylic methacrylate resin, such as BR-201 (a butyl methacrylate thermoplastic acrylic resin) supplied by Dianal America, Inc., formulated in a solvent system comprising propylene glycol methyl ether acetate, propylene glycol methyl ether and diacetone alcohol. Typically, the solvent system is first prepared by transferring specified solvents or equivalents to an appropriate mixing vessel. The release agent such as a silicone-free, fluorocarbon-modified polymer may then be added and the solution mixed. The solution is then heated to approximately 140° F. or typically at least to the resin melting point (BR-210 typically melts at temperatures from 110 to 120° F.). The resin is then added while mixing the solution, as is the plasticizer. The resulting formulation is stirred until components are in solution and thoroughly mixed. An acceptable commercial plasticizer includes Paraplex G-60 supplied by The C.P. Hall Company. An acceptable release and flow agent includes EFKA-7375 supplied by EFKA Additivies B.V., the Netherlands.
- Yet a further embodiment of the
transfer medium 104 may be prepared by adding 3% by weight of the release agent identified above as Additol VXL 6383 in accordance the following formulation scheme: -
TABLE 8 Alternative Transfer Medium Formulation Component % by weight range Acrylic methacrylate resin 27.52 Plasticizer 8 Release agent (EFKA-7375) 3 Release agent (Additol VXL 6383) 3 Solvent system comprising: Propylene glycol methyl ether acetate 36.12 Propylene glycol methyl ether 13.76 Diacetone alcohol 8.6 - Dispersion of solids in the above formulations may be evaluated using a grind block or smear test. Preferably, mixing is performed until solids are tested as being under approximately 3 microns in size.
- Once formed, an
ink transfer system 100 may be stored until needed. Thedecal 109 may be transferred to afinal substrate 101, such as a pre-painted automotive body part, according to the method or steps set forth below. - First, the
ink transfer system 100 is trimmed, if desired, to removeexcess backing sheet 102 material. Generally, cutting or trimming of thetransfer medium 104 should be avoided unless it extends sufficiently beyond the margins of thebase coat 106 andink layers 108 to allow removal of excess. Next, theink transfer system 100 is soaked in water for several minutes, two or more minutes generally sufficing for relatively small decals. Extended periods of soaking should be avoided as the water soluble coating on thebacking sheet 102 may dissolve sufficiently to cause thedecal 109 and transfer medium 104 layers to fall away from thebacking sheet 102. -
FIG. 6 is a top perspective view of the lower edge of thebacking sheet 102 positioned against afinal substrate 101 with theink transfer system 100 facing the viewer. Thedecal 109 including the attachedtransfer medium 104 is then slid off of thebacking sheet 102. InFIG. 7 , thedecal 109 has been slid partially off of thebacking sheet 102 and onto the surface of thesubstrate 101. - At this point, the
decal 109 is held together by the strong adhesion of thebase coat 106, ink layers 108, andrelease coat 110 to one another and the weaker, though sufficient, adhesion of thetransfer medium 104 to therelease coat 110. As indicated above, thetransfer medium 104 is not composed of the same material as theink 108 and, although flexible and capable of stretching, it is less so than therelease coat 110,ink 108 andbase coat 106 layers since it is designed to provide dimensional stability during transfer of thedecal 109. For these purposes thetransfer medium 104 is also typically screen printed or otherwise deposited to form a somewhat thicker layer. - The
ink transfer decal 109 is applied to thesubstrate surface 101 with thetransfer medium 104 on top and thebase coat 106 contacting thesubstrate surface 101. Due to the moisture on the decal 109 (the substrate may also be prewetted, for example by spraying with water from a spray bottle or hose, not shown) and the thinness and flexibility of thedecal 109, the surface tension of the water between thedecal 109 and thesubstrate 101 causes thedecal 109 to conform closely to thesubstrate surface 101 and to loosely adhere. At this point thedecal 109 may be moved or adjusted to its final position, often determined by registration marks (not shown) on thesubstrate 101, and any wrinkles or bubbles may be smoothed out using a squeegee, sponge or other appropriate device. - In
FIG. 8 , thedecal 109 is shown fully removed from thebacking sheet 102 and placed in final position upon thesubstrate surface 101. InFIGS. 6 through 7 , the dashed lines defining theink 108 andbase coat 106 layers indicate that these layers are covered by and viewed through thetransfer medium 104. - Because the
ink 108 andbase coats 106 are prepared from linear chain polyester polyurethanes, and polymerization is somewhat suppressed through use of antioxidants, theink 108 andbase coat 106 films of thedecal 109 are extremely flexible and exhibit high elongation characteristics. Elongation of over 400% may be obtained when stretching theink 108 and base coats 106. Because of these properties, thedecal 109 may be applied to molded surfaces having irregular shapes. Thetransfer medium 104 allows for stretching and other manipulation of thedecal 109 during application to thesubstrate 101 while aiding in handling of thedecal 109 which would otherwise be difficult due to the extreme thinness of theink 108 andbase coat 106 layers. In other applications, thedecal 109 may be transferred to a relatively flat surface for ease of registering and then subjected to considerable stretching and elongation due to bending or stamping of the piece post-transfer. - The
decal 109 is then allowed to dry through air drying or other means. After thedecal 109 andtransfer medium 104 dries and substantially all surface moisture has evaporated, typically 1 to 24 hours after transfer, thetransfer medium 104 may be peeled away from the depositeddecal 109.FIG. 9 provides a top perspective view of thedecal 109 showing a portion of thetransfer medium 104 peeled away from thedecal 109 andsubstrate 101. Because it is removed after the water between thedecal 109 and thesubstrate 101 has evaporated, it is important that thetransfer layer 104 not stick or bind to thedecal 109 excessively.FIG. 10 illustrates thedecal 109 after removal of thetransfer medium 104. At this point in the transfer process aclear base coat 106 may still be slightly visible or discernable from the surrounding surface of thesubstrate 101. - After 12 to 24 hours or air drying the water has typically evaporated from the
decal 109 andsubstrate 101 completely and a clear coat may be applied. A commonly used, solvent-based, thermoset clear coat is typically applied by spraying. Such clear coatings often comprise thermoset polyurethanes that must go through a heat conversion to complete polymerization. Because of the extensive polymerization and crosslinking such coatings typically provide very good chemical resistance. As an alternative to a heat set system, a photoreactive (UV) coating may be applied. -
FIG. 11 is a top perspective view of thedecal 109 after application of the clear coat and baking. At this point in the ink transfer process, thedecal 109 has fused to thesubstrate 101 and clear coat and, due to the thinness of thebase coat 106 andink 108 layers, presents a design that does not protrude or project above the adjacent finish. - The
substrate 101 bearing thedecal 109 and overlying clear coat is then baked in an oven or otherwise heated to temperatures typically in the range of 250 to 325 degrees Fahrenheit. Due to the presence of antioxidants, theink 108 andbase coat 106 films may readily withstand exposure to such temperatures without degradation, discoloration, shrinkage, peeling or other defects. During the baking cycle thedecal 109 softens becoming fluid or semi-fluid. While heated thedecal 109 further polymerizes and adheres to compatible underlying surfaces such as typical polyurethane-based paints and coatings used in the automotive industry. The softening and adherence characteristics of thedecal 109 are typically achieved as the temperature during the baking cycle rises to 185° F. and continue to improve as the temperature increases to 265° F. Thedecal 109 may be subjected to temperatures in excess of 375° F. - The ink film forming mechanism employed in the above ink embodiments is partially that of a solvent evaporative coating yielding a thermoplastic ink film. Film formation occurs during evaporation of the diluents and the concomitant coalescence of the polymer chains. Polymerization to form linear, polyester-based polyurethane chains yields an ink film having thermoplastic characteristics while still exhibiting good resistance to solvents and other chemicals after curing.
- If further chemical resistance, more complete polymerization and/or enhanced abrasion resistance of the
base coat 106 and ink layers 108 is desired, free isocyanates may be added to the ink formulation. Free isocyanates with particular advantages include aliphatic polyisocyanate resins based on hexamethylene diisocyanate. Such compounds react well with polyester hydroxyl-functional coreactants such as are used to prepare the vehicle described in Table 1. Resultant coatings prepared using polyisocyanate compounds exhibit enhanced resistance to solvents and oxidizing chemicals as well as increased abrasion resistance. The coatings have enhanced light stability, resistance to heat degradation and resist yellowing or other discoloration. A commercial product appropriate for providing free isocyanates with the above advantages includesDesmodur N 100, produced by Bayer Polymers LLC. Typically, these products are added to the ink formulation at levels of 0.005 to 0.01% of resin solids. - As a further embodiment, a thermal set ink transfer system may be provided through the addition to the
ink 108 andbase coat 106 formulations of melamine and an acid catalyst. The melamine reacts with the acid catalyst to form crosslinkages that set the film, reducing or eliminating thermoplasticity but increasing chemical and heat resistance. - It is to be understood that while certain forms of this invention have been illustrated and described, it is not limited thereto except insofar as such limitations are included in the following claims and allowable equivalents thereof.
Claims (30)
1. A coating transfer system comprising:
a flexible backing sheet having a surface adapted to releaseably receive polymer resins; and
an ink transfer coating printed upon a portion of said sheet, said ink transfer coating comprising a thermoplastic polymer resin, a UV stabilizer to inhibit photo degradation of polymers formed from said resin, and an antioxidant to inhibit oxidative degradation of polymers formed from said resin, said ink transfer coating being releaseably received on said sheet,
said system being constructed without a separately applied adhesive.
2. The coating transfer system of claim 1 , wherein said resin comprises a member selected from the group consisting of aliphatic polyurethanes, polyester-based polyurethanes, the reaction product of at least one diisocyanate and a polyol, and diphenylmethane diisocyanates.
3. The coating transfer system of claim 1 , wherein said resin comprises at least one component selected from the group consisting of 4,4′ diphenylmethane diisocyanate, 4,2′ diphenylmethane diisocyanate and 2,2′ diphenylmethane diisocyanate.
4. The coating transfer system of claim 1 , wherein said UV stabilizer comprises a UV absorbing compound.
5. The coating transfer system of claim 1 , wherein said UV stabilizer comprises a hindered amine.
6. The coating transfer system of claim 1 , wherein said UV stabilizer is selected from the group consisting of hydroxyl substituted benzophenones and hydroxyl substituted benzotriazoles.
7. The coating transfer system of claim 1 , wherein said UV stabilizer is selected from the group consisting of hydroxyphenyl-benzotriazoles, hydroxyphenyl-triazines, hydroxy-benzophenones and oxalic anilides.
8. The coating transfer system of claim 1 , wherein said UV stabilizer comprises a hindered amine light stabilizer derived from a member selected from the group consisting of 2,2,6,6-tetraalkyl piperidine, a substituted piperizinedione, and decanedioic acid.
9. The coating transfer system of claim 1 , wherein said antioxidant comprises a sterically hindered phenolic compound.
10. The coating transfer system of claim 1 , wherein said ink transfer coating softens and adheres to a receiving substrate when said ink transfer coating is heated to a temperature between 185° F. and 375° F.
11. The coating transfer system of claim 1 , further comprising a release layer deposited upon said ink transfer coating.
12. The coating transfer system of claim 1 , said ink transfer coating further comprising free isocyanate compounds.
13. The coating transfer system of claim 1 , said flexible backing sheet being water slide decal paper.
14. The coating transfer system of claim 1 , said ink transfer coating comprising one or more separately applied ink layers, each of said one or more ink layers being formed by printing a solvent-containing ink onto said sheet, said ink being capable of drying by solvent evaporation at ambient conditions within one hour of application to said sheet.
15. The coating transfer system of claim 14 , said ink transfer coating further comprising a transparent base coat in addition to said one or more ink layers.
16. The coating transfer system of claim 1 , wherein said ink transfer coating may be stretched to elongate greater than 400%.
17. The coating transfer system of claim 1 , wherein after removal of said backing sheet and after said ink transfer coating is placed in contact with a pre-painted substrate and heated to a temperature of 185° F. or above, polymers formed from said resin migrate into said substrate thereby permanently bonding said ink transfer coating with said pre-painted substrate without a separately applied adhesive.
18. A method of transferring a solid ink design to a substrate comprising the steps of:
(a) providing a decal that does not include a separately applied adhesive, said decal comprising—
(i) a flexible backing sheet having a surface adapted to releaseably receive polymer resins, and
(ii) an ink transfer coating comprising one or more ink layers and, optionally, a transparent base coat, each of said one or more ink layers and optional base coat being printed onto said sheet as a liquid comprising a thermoplastic polymer resin, a UV stabilizer to inhibit photo degradation of polymers formed from said resin, an antioxidant to inhibit oxidative degradation of polymers formed from said resin, and a solvent system, said liquid from which any of said one or more ink layers and optional base coat are formed being capable of drying on said sheet by solvent evaporation upon being allowed to dry for one hour at ambient conditions;
(b) removing said flexible backing sheet from said decal to expose a surface of said ink transfer coating; and
(c) applying said exposed surface to said substrate.
19. The method according to claim 18 , said flexible backing sheet comprising water slide decal paper.
20. The method according to claim 19 , step (b) including wetting said backing sheet prior to removing said backing sheet from said decal.
21. The method according to claim 20 , step (b) including removing excess moisture from between said ink transfer coating and said substrate.
22. The method according to claim 21 , step (b) including drying substantially all surface moisture from said decal.
23. The method according to claim 1 , said method further comprising:
(d) applying a clear coat over said substrate and said ink transfer coating after step (c) with no raised transition between said substrate and said ink transfer coating being perceptible to the touch or to the naked eye after said clear coat application.
24. The method according to claim 23 , after step (d), baking said clear coat at a temperature of between 250 to 325° F. thereby fusing said ink transfer coating to said substrate and said clear coat.
25. The method according to claim 19 , said substrate being a surface of a vehicle or vehicle accessory.
26. The method according to claim 19 , said substrate being pre-painted prior to application of said decal.
27. The method according to claim 19 , said substrate being a flat surface.
28. The method according to claim 27 , further comprising:
(e) bending, stamping or otherwise shaping said substrate surface after application of said decal thereby causing said ink transfer coating to stretch and elongate without cracking.
29. The method according to claim 19 , said surface being a contoured surface.
30. The method according to claim 29 , further comprising:
(f) stretching said decal over said contoured surface after removing said backing sheet without wrinkling or damaging the decal.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/813,870 US20100243140A1 (en) | 2005-02-08 | 2010-06-11 | Thermally Reactive Ink Transfer System |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/053,542 US7758949B1 (en) | 2005-02-08 | 2005-02-08 | Thermal reactive ink transfer system |
US12/813,870 US20100243140A1 (en) | 2005-02-08 | 2010-06-11 | Thermally Reactive Ink Transfer System |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/053,542 Continuation US7758949B1 (en) | 2005-02-08 | 2005-02-08 | Thermal reactive ink transfer system |
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US20100243140A1 true US20100243140A1 (en) | 2010-09-30 |
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Family Applications (3)
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US11/053,542 Active US7758949B1 (en) | 2005-02-08 | 2005-02-08 | Thermal reactive ink transfer system |
US11/558,009 Active US7547372B1 (en) | 2005-02-08 | 2006-11-09 | Thermally reactive ink transfer system |
US12/813,870 Abandoned US20100243140A1 (en) | 2005-02-08 | 2010-06-11 | Thermally Reactive Ink Transfer System |
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US11/053,542 Active US7758949B1 (en) | 2005-02-08 | 2005-02-08 | Thermal reactive ink transfer system |
US11/558,009 Active US7547372B1 (en) | 2005-02-08 | 2006-11-09 | Thermally reactive ink transfer system |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20170326906A1 (en) * | 2014-12-24 | 2017-11-16 | 3M Innovative Properties Company | Design transfer sheet, and decorative film, and method for producing same |
CN108538762A (en) * | 2018-04-24 | 2018-09-14 | 京东方科技集团股份有限公司 | Display master blank and preparation method, display base plate and preparation method, display device |
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JP2021088095A (en) * | 2019-12-03 | 2021-06-10 | 川崎重工業株式会社 | Transfer sheet, design product, and method of manufacturing design product |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060246266A1 (en) * | 2005-04-29 | 2006-11-02 | Modernistic, Inc. | Ultra thin graphics and methods |
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US11397382B2 (en) * | 2019-06-07 | 2022-07-26 | Korea Advanced Institute Of Science And Technology | Method for selective delamination and transfer of thin film using liquid platform |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3978156A (en) * | 1975-05-14 | 1976-08-31 | The B. F. Goodrich Company | Color stabilized polyurethanes |
US4337289A (en) * | 1977-11-02 | 1982-06-29 | Reed Kenneth J | Water release transfer |
US4472537A (en) * | 1982-09-17 | 1984-09-18 | Corning Glass Works | Thermoplastic inks for decorating purposes |
US5073423A (en) * | 1990-01-04 | 1991-12-17 | Corning Incorporated | Decalcomania |
US5981077A (en) * | 1996-05-29 | 1999-11-09 | Ricoh Company, Ltd. | Image transfer sheet and image forming method therefor |
US6200666B1 (en) * | 1996-07-25 | 2001-03-13 | 3M Innovative Properties Company | Thermal transfer compositions, articles, and graphic articles made with same |
US20010051265A1 (en) * | 1996-11-04 | 2001-12-13 | Williams Scott A. | Heat-setting label sheet |
US20030088045A1 (en) * | 2000-02-15 | 2003-05-08 | Hans Haberle | Use of aqueous polyurethane dispersions in formulations for crack sealing coating systems |
US6623817B1 (en) * | 2001-02-22 | 2003-09-23 | Ghartpak, Inc. | Inkjet printable waterslide transferable media |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH538366A (en) * | 1971-08-13 | 1973-06-30 | Mueller Hans Grapha Masch | Device for gluing inserts to printed sheets |
US3826701A (en) * | 1972-10-31 | 1974-07-30 | Us Army | Controllable heat sealing process for optimum seal strength |
JPS58145490A (en) | 1982-02-19 | 1983-08-30 | Sumitomo Suriim Kk | Marking material |
US4770732A (en) * | 1983-08-01 | 1988-09-13 | Minnesota Mining And Manufacturing Company | Transfer method for applying graphics to a display surface |
US5032449A (en) * | 1989-01-26 | 1991-07-16 | Af Strom Oscar R F | Decals and processes for transfer of images to substrates |
US5203941A (en) * | 1989-10-19 | 1993-04-20 | Avery Dennison Corporation | Process for manufacturing plastic siding panels with outdoor weatherable embossed surfaces |
US5167995A (en) * | 1990-06-08 | 1992-12-01 | Minnesota Mining And Manufacturing Company | Low temperature shock resistant release liner |
US6548618B2 (en) * | 1993-06-01 | 2003-04-15 | Spalding Sports Worldwide, Inc. | Golf ball having dual core and thin polyurethane cover formed by RIM |
JPH07186597A (en) | 1993-12-27 | 1995-07-25 | Sakura Color Prod Corp | Transferring paper |
IT1288217B1 (en) * | 1996-04-24 | 1998-09-11 | Giuseppe Billoni | METHOD OF PREPARATION AND APPLICATION FOR TRANSFER ON ANY SUPPORT OF ORNAMENTAL, DECORATIVE, ADVERTISING AND |
US5851614A (en) | 1996-12-10 | 1998-12-22 | Buck; Ronald Mark | Self-adhesive opaque dry transfer decals |
US6641257B1 (en) | 1998-05-29 | 2003-11-04 | American Ink Jet Corporation | Lightfast ink jet inks |
US6467893B1 (en) | 1998-12-28 | 2002-10-22 | Fuji Photo Film Co., Ltd. | Method and apparatus for forming image with plural coating liquids |
US6743109B2 (en) * | 2000-04-10 | 2004-06-01 | Brunswick Bowling & Billards Corporation | Decorative bowling ball and method therefor |
DK1229090T3 (en) | 2001-02-05 | 2003-08-18 | Sicpa Holding Sa | A polyurethane resin, a coating composition comprising a polyurethane resin, use of a polyurethane resin for printing plastic substrates, a process for producing a polyurethane resin, a process for producing a ........ |
US6734273B2 (en) | 2001-02-12 | 2004-05-11 | Noveon Ip Holdings Corp. | High molecular weight thermoplastic polyurethanes made from polyols having high secondary hydroxyl content |
US6654040B2 (en) * | 2001-04-26 | 2003-11-25 | Hewlett-Packard Development Company, L.P. | Method for creating durable electrophotographically printed color transparencies using clear hot stamp coating |
US6797748B2 (en) | 2001-06-08 | 2004-09-28 | Bic Corporation | Polyurethane based inks for writing instruments |
US6964722B2 (en) * | 2002-08-07 | 2005-11-15 | Trio Industries Holdings, L.L.C. | Method for producing a wood substrate having an image on at least one surface |
US20040161564A1 (en) | 2003-02-14 | 2004-08-19 | Truog Keith L. | Dry paint transfer laminate |
-
2005
- 2005-02-08 US US11/053,542 patent/US7758949B1/en active Active
-
2006
- 2006-11-09 US US11/558,009 patent/US7547372B1/en active Active
-
2010
- 2010-06-11 US US12/813,870 patent/US20100243140A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3978156A (en) * | 1975-05-14 | 1976-08-31 | The B. F. Goodrich Company | Color stabilized polyurethanes |
US4337289A (en) * | 1977-11-02 | 1982-06-29 | Reed Kenneth J | Water release transfer |
US4472537A (en) * | 1982-09-17 | 1984-09-18 | Corning Glass Works | Thermoplastic inks for decorating purposes |
US5073423A (en) * | 1990-01-04 | 1991-12-17 | Corning Incorporated | Decalcomania |
US5981077A (en) * | 1996-05-29 | 1999-11-09 | Ricoh Company, Ltd. | Image transfer sheet and image forming method therefor |
US6200666B1 (en) * | 1996-07-25 | 2001-03-13 | 3M Innovative Properties Company | Thermal transfer compositions, articles, and graphic articles made with same |
US20010051265A1 (en) * | 1996-11-04 | 2001-12-13 | Williams Scott A. | Heat-setting label sheet |
US20030088045A1 (en) * | 2000-02-15 | 2003-05-08 | Hans Haberle | Use of aqueous polyurethane dispersions in formulations for crack sealing coating systems |
US6623817B1 (en) * | 2001-02-22 | 2003-09-23 | Ghartpak, Inc. | Inkjet printable waterslide transferable media |
Non-Patent Citations (1)
Title |
---|
Dow Ethocel product information * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170326906A1 (en) * | 2014-12-24 | 2017-11-16 | 3M Innovative Properties Company | Design transfer sheet, and decorative film, and method for producing same |
US10774242B2 (en) * | 2014-12-24 | 2020-09-15 | 3M Innovative Properties Company | Transfer sheet, and decorative film, and method for producing same |
CN108538762A (en) * | 2018-04-24 | 2018-09-14 | 京东方科技集团股份有限公司 | Display master blank and preparation method, display base plate and preparation method, display device |
US11094894B2 (en) | 2018-04-24 | 2021-08-17 | Boe Technology Group Co., Ltd. | Method for manufacturing a display motherboard |
CN109148530A (en) * | 2018-08-20 | 2019-01-04 | 武汉华星光电半导体显示技术有限公司 | A kind of production method of organic light emitting diode display |
US10818855B2 (en) | 2018-08-20 | 2020-10-27 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Method of manufacturing an organic light emitting diode display |
CN109148337A (en) * | 2018-08-31 | 2019-01-04 | 京东方科技集团股份有限公司 | The preparation method of display base plate |
US11018328B2 (en) | 2018-08-31 | 2021-05-25 | Boe Technology Group Co., Ltd. | Method and apparatus for manufacturing display substrate |
JP2021088095A (en) * | 2019-12-03 | 2021-06-10 | 川崎重工業株式会社 | Transfer sheet, design product, and method of manufacturing design product |
JP7269867B2 (en) | 2019-12-03 | 2023-05-09 | カワサキモータース株式会社 | Transfer sheet, design product, and design product manufacturing method |
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US7547372B1 (en) | 2009-06-16 |
US7758949B1 (en) | 2010-07-20 |
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