Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
  • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
  • B44C1/17—Dry transfer
  • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
• • 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
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2813—Heat or solvent activated or sealable
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2813—Heat or solvent activated or sealable
  • Y10T428/2817—Heat sealable
  • Y10T428/2826—Synthetic resin or polymer
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating
• • 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]
  • Y10T428/31536—Including interfacial reaction product of adjacent layers
• • 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.]
  • Y10T428/31609—Particulate metal or metal compound-containing
  • Y10T428/31612—As silicone, silane or siloxane

Definitions

• ABSTRACT A method of and articles for decorating heat resistant surfaces such as glass or metal using a heat transfer decoration comprising in sequence a temporary carrier, a transfer lacquer layer which is removably adhered to the surface of said carrier, at least one design print layer adhered over the lacquer layer and a heatactivatible adhesive layer adhered over said design print layer wherein at least the transfer lacquer and design print layers contain cross-linkable resin means and a cross-linking agent for cross-linking the resin intralayer and interlayer to form a unified adherent decoration resistant to abrasion and chemicals.
• the metal or glass surface may optionally be coated with a crosslinkable primer composition prior to application of the heat transfer decoration thereto.
• thermoset label by employing in one or more of the layers of the transfer label certain polymerizable crosslinking agents which are capable, preferably in response to heat, of crosslinking the resins in adjacent layers to form strong, cohesive interlayer chemical bonds, chemical, abrasion and rub resistance are ture insensitive, so that glass, ceramic or metal containers bearing the thermoset label can be subjected to high temperatures without deleterious effects on the labels properties.
• the present invention can be used with particular advantage in multilayer decorative transfer labels such as those disclosed in copending U.S. Pat. application Ser. No. 244,292, filed Apr. 14, 1972, by B. Asnes, incorporated herein by reference.
• a heat transfer label system is described which comprises an adhesive layer, laid down and adhered to a design print, which has been laid down and adhered to a transfer lacquer layer, (first down lacquer), which has been laid down and releasably adhered to a release layer, which layer may or may not have a backing sheet or layer adhered to it.
• the transfer lacquer layer is preferably a clear cellulosic resin, such as a cellulosic ester, having a softening point well above 300F to 450F, i.e. a cellulosic resin which does not appreciably soften or tackify at transfer temperatures.
• the design print layer is made up of one of more colors of conventional heat transfer inks such as nitrocellulose and/or polyamide inks, containing dispersed or dissolved therein pig ments and/or dyes of the colors desired.
• the last down adhesive layer is made up of a conventional heatactivatable adhesive, suitable adhesives being disclosed therein.
• crosslinking agent is used to designate a material which chemically reacts, e.g. polymerizes, with crosslinkable polymerizable material to form chemical bonds, i.e. crosslinkages, between the polymer molecular chains of that material or between the polymer molecular chains of that material and a different material.
• the different material may include polymer chains or parts of chains of the crosslinking agent itself, i.e., during polymerization the crosslinking agent itself may form polymer chains which may be themselves crosslinked by the crosslinking agent and/or crosslinked with another or other crosslinkable materials by the crosslinking agent.
• the preferred embodiment utilizes several polymeric crosslinking agents which react with polymeric crosslinkable materials.
• crosslinking as used herein includes the formation of chemical bonds between the chain of the crosslinking agent and/or the chains of one or more crosslinkable materials.
• both the crosslinkable material and the crosslinking agent take an active part in any reaction which occurs between them, and the term crosslinking agent is used more or less to conveniently designate the more reactive of the two materials.
• some materials are suitable as both the crosslinkable material and the crosslinking agent, e.g., those polymers which undergo substantial crosslinking with themselves at elevated temperatures.
• Crosslinking agents suitable for use in accordance with the invention are well known in the art. Choice of a particular crosslinking agent depends upon which layer it is to be used in, and the nature of the material in the adjacent layer, or layers, it is desired to crosslink. If the crosslinking agent is used in the first down or transfer lacquer layer, it must not reduce the release properties of the lacquer/release layer interface. Accordingly it should have a sufficiently high .melting point to keep from becoming soft or tacky at the temperatures at which the label will be transferred, lest it adhere to the release layer and interfere with release. Also, it should not crosslink or otherwise be reactive with the material in the release sheet, which would also prevent good release. If the crosslinking agent is used in the adhesive layer, it must not interfere with the necessary adhesive properties of that layer.
• suitable crosslinking agents include those having blocked isocyanate groups, epoxy groups, urea formaldehyde groups, including substituted urea formaldehyde groups, primary and secondary amines and polyamines, and other materials known in the art. Crosslinking will also occur between materials having available urea formaldehyde groups and materials having available epoxy groups; between materials having available urea formaldehyde groups and materials having available carboxyl groups; between blocked isocyanates and materials containing epoxide groups; etc.
• crosslinking agents suitable for crosslinking particular polymeric materials are known to those skilled in the art, those dealt with herein being only exemplary.
• blocked isocyanates reaction products of isocyanates with active hydrogen containing compounds which result in an addition product having only limited thermal stability. These compounds are stable at room temperature, but react at elevated temperatures as if an isocyanate were present.
• Suitable blocked isocyanates are known in the art, as disclosed for example in Sanders & Frisch, Polyurethanes, Chemistry & Technology, Vol. 1, pp. 1 18-21 (1962).
• Suitable blocking agents include those disclosed therein, such as the phenols, substituted phenols, alkyl and aryl mercaptans, and other compounds having reactive hydrogen, such as the alcohols.
• blocked isocyanates suitable for use in the present invention include a variety of Aminimides available from Ashland Chemical Co., especially Ashland Aminimide 2l00l (bis (trimethylamine) sebacimide) and Ashland Aminimide 20603 (Bis (dimethyl-Z-hydroxypropylamine) adipimide), and a caprolactam blocked polymeric isocyanate available under the mark lsonate 123? from the Upjohn Company.
• material containing blocked isocyanate groups is used as a crosslinking agent in the transfer lacquer layer of a multi-layer decorative label, and the adjacent design print layer contains a polymeric material containing available hydroxyl groups.
• the transfer lacquer layer also contains a polymeric material having available hydroxyl groups.
• Suitable polymers having available hydroxyl groups include known polyols, such as cellulose and modified cellulosic materials such as cellulose esters, including cellulose acetate, cellulose propionate, cellulose acetate butyrate, etc., substituted cellulosic materials such as hydroxyalkyl cellulose; starches, both unmodified and modified; polymeric resins based on alcohols, such as polyvinyl alcohol, or on monomers having a plurality of hydroxyl groups, such as diols and glycols; and other polyols well known in the art. It is preferred to use a cellulosic material as the source of hydroxyl substituents in the transfer lacquer layer, preferably cellulose esters such as cellulose acetate.
• the amounts of the reactive components included in the various layers can vary considerably, depending upon the particular types of materials used and the properties desired of them in use.
• the transfer lacquer layer may be predominantly made up of crosslinkable material, such as the cellulose ester, and contain a relatively small amount of a crosslinking agent, such as the blocked isocyanates. Thus it may contain from about to about 99 percent by weight cellulose acetate or other cellulosic material and from about 0.5 to about 20 percent by weight blocked isocyanates. Preferably that layer contains about to percent by weight cellulose acetate or other cellulose ester and between about 5 to about 15 percent polyisocyanate material.
• Other materials may also be incorporated in the transfer lacquer layer, such as a small amount of a tracer compound which is normally colorless but fluoresces under the influence of ultraviolet radiation. The tracer compound is useful in the printing process to facilitate the registration of clear lacquers.
• those layers which are separated from the release layer by the transfer lacquer layer or other layers the reactivity and physical characteristics are not as critical as they are in the transfer layer, since adherance to the release layer is not a problem.
• those layers may be formulated with a view to optimizing both intralayer cohesion and interlayer adhesion.
• the adhesive bond between layers in the decoration of the present invention may be referred to as a cohesive bond or cohesion, since the crosslinking which occurs between the materials in adjacent layers in effect creates an interlayer blend of chemically linked material.
• materials can be used which are much more reactive than those used in the transfer lacquer layer.
• the design print layers contain both a crosslinkable material, such as a material having available hydroxyl groups, and a crosslinking agent, such as a urea-formaldehyde resinous material.
• the relative amounts of each can be about the same, or either may predominate.
• the design print layers contain from about to 55 percent by weight polyol and from about 40 to 65 percent by weight heat reactive urea formaldehyde binder.
• the decoare substituted ureaformaldehydes such as butylated urea formaldehyde material.
• the polyol in the design print layers is preferably a hydroxyl modified vinyl resin, a hydroxyl modified vinyl chloride-vinylacetate copolymer being most preferred.
• the design print layers will also contain the pigments necessary for the desired color, and minor amounts of other additives known in the art may be added.
• the adhesive layer is crosslinked with its adjacent print layer, in accordance with the invention, it must both act as an adhesive to bind the decoration to the glass, ceramic, metal or other substrate, and serve as a crosslinked, integrated layer in the finished decoration.
• it is a heat activatable adhesive, and the same materials which make it a heat activatable adhesive also participate-in the crosslinking between the adhesive layer and the adjacent design print layers.
• these may comprise one or more crosslinkable materials and one or more crosslinking agents.
• the crosslinkable material in the adhesive layer comprises a carboxyl modified vinyl resin
• the adhesive layer further comprises two epoxy type crosslinking agents: an epoxy modified vinyl resin and a highly reactive diglycidyl ether-bisphenol A type of polyepoxide.
• Other additives may also be included, such as a small amount of an ultraviolet radiation absorber, which permits the adhesive layer to be easily distinguished from the transfer lacquer layer during printing.
• the amounts required of the various ingredients depend upon the particular ingredients used in the system.
• the preferred embodiment contains between about 60 percent of the epoxy modified vinyl resin, from I to 15 percent of the diglycidyl etherbisphenol A polyepoxide, and from 35 60 percent of the carboxyl modified vinyl resin.
• the decorative label is made by forming a suitable release layer, as, for example, in the manner described in the above mentioned co-pending U.S. Pat. application Ser. No. 244,292 by B. Asnes.
• the transfer lacquer layer is applied onto the release layer, preferably by roto gravure printing.
• the design print and adhesive layers are thereafter laid down sequentially over the transfer lacquer layer, also preferably by printing techniques.
• the substrate is first treated with any of the well known silane adhesion promoters.
• silane adhesion promoters include epoxy silanes (e.g., A- 187, from Union Carbide) mercapto silanes (e.g., A- 189, also from Union Carbide), and others.
• pre-heat the substrate Generally, pre-heating temperatures from about 150F to about 250F have been found to be advantageous.
• the decorative label is put in contact with the heated substrate and heat and pressure are applied to the temporary backing which supports the release layer, to effect pressing of the adhesive layer against the substrate surface.
• a heat transfer decorating machine preferably the Dennison TDlB Decorating Machine, described in several U.S. Patents including U.S. Pat. Nos. 2,862,832, 3,064,714, 3,231,448 and rated substrate is heat cured, e.g. for 10 to 20 minutes at about 200300F, and then it may be further heat cured, e.g., for 10 to 20 minutes at about 350-450F.
• the benefits provided by the present invention are outstandingi'lbe applied decorative labels are far superior in durability, abrasion and mar resistance, ease of application and appearance to heat transfer labels previously known
• One of the most important advantages obtained through the present invention is the increase in decorating speed. With even the most efficient of comparable previous systems, the labeling speeds were limited to about 20 or, at most, about 30 bottles per minute. Speeds of between and bottles per minute have been achieved using the present invention, with the decorated bottles having the improved appearance, chemical and abrasion resistance previously mentioned.
• crosslinking and/or crosslinkable materials be used to obtain the reactions between adjacent layers
• benefits can be derived from much simpler systems in accordance with this invention.
• a two component reactive system might be used in which the same crosslinking agent,.for example, a blocked isocyanate material, is contained in both the transfer lacquer layer and in the adhesive layer, and reacts from both directions with a single crosslinkable material in the design print layer, e.g., a polyol.
• the same crosslinking agent would also work if the crosslinking agent were in the design print layer and the crosslinkable materials are in the transfer lacquer and adhesive layers.
• each layer contain both a crosslinkable material and a crosslinking agent.
• the intralayer cohesion is improved by crosslinking between the materials within each layer; and the interlayer cohesion, and thus the overall cohesion of the label, is improved by the action of the crosslinking agents in both adjacent layers.
• the decoration becomes thermoset, both throughout each layer and between layers, as discussed above.
• some benefit is obtained even when one or more of the layers contains only one of the reactive materials, whether it be a crosslinkable material or a crosslinking agent.
• all of the transfer lacquer layer, the design printlayer or layers and the adhesive layer contain both crosslinkable and crosslinking: materials.
• the preferred crosslinkable material is cellulose acetate, and the preferred crosslinking agent is Isonate 123P, a caprolactam blocked polymeric isocyanate available from the Upjohn Company.
• the preferred crosslinkable material is a hydroxyl modified vinyl chloride-vinylacetate resin and the preferred crosslinking agent is butylated urea-formaldehyde polymeric material.
• the preferred crosslinkable, material is a carboxyl modified vinylchloride-vinylacetate resin, and two epoxy crosslinking agents are preferably used, namely, an epoxy modified vinylchloride-vinylacetate copolymer resin and a diglycidyl ether-bisphenol A type of polyepoxide.
• two epoxy crosslinking agents are preferably used, namely, an epoxy modified vinylchloride-vinylacetate copolymer resin and a diglycidyl ether-bisphenol A type of polyepoxide.
• the polyisocyanate in the transfer lacquer layer becomes unblocked and reacts both with the hydroxyl groups of the cellulose acetate in the transfer lacquer layer and the hydroxyl groups of the hydroxyl modified resin in the design print layer.
• the butylated urea-formaldehyde in the design print layer reacts with the same hydroxyl groups in the transfer lacquer and design print layers, and also with both of the epoxides and also the carboxyl groups in the adhesive layer.
• the hydroxyl groups of the hydroxyl modified resin in the design print layer reacts with the now unblocked polyisocyanate in the transfer lacquer layer, with the butylated ureaformaldehyde in its own design print layer and with both of the epoxy compounds in the adhesive layer.
• This system involving various crosslinking agents and crosslinkable materials gives a particularly strong, cohesive, mar resistant, decorative label.
• EXAMPLE 1 A heat transfer decoration was prepared by printing on a suitable release surface as described in the abovementioned U.S. Pat. application, Ser. No. 244,292 by B. Asnes, a multiple layer print applied by roto gravure, comprising a clear lacquer composed of cellulose acetate, 9.8 parts, (E-398-3, made by Eastman Chemical Products, Inc.) dissolved in 80 parts of methyl ethyl ketone and 8.9 parts acetone, and containing 0.4 parts of a fluorescent dye (a substituted phenyl benzotriazole sold under the name lntrawite OB by Intracolor Corporation) and 1.0 parts of blocked polymeric isocyanate, (lsonate 123P, by Upjohn Co.).
• a fluorescent dye a substituted phenyl benzotriazole sold under the name lntrawite OB by Intracolor Corporation
• blocked polymeric isocyanate (lsonate 123P, by Upjohn Co.).
• the design print using a reactive yellow ink consisting of 15.3 parts butylated urea-formaldehyde resin solution (Resimene U-920, by Monsanto), 11.5 parts hydroxyl modified vinylchloride-vinylacetate copolymer resin (VAGD, by Union Carbide) dissolved in 12.5 parts ethyl acetate, 34.2 parts n-propyl acetate, 16.6 parts toluol, and 3.2 parts isopropanol, and containing 0.1 parts silicone resin (S-10, Union Carbide).
• a reactive yellow ink consisting of 15.3 parts butylated urea-formaldehyde resin solution (Resimene U-920, by Monsanto), 11.5 parts hydroxyl modified vinylchloride-vinylacetate copolymer resin (VAGD, by Union Carbide) dissolved in 12.5 parts ethyl acetate, 34.2 parts n-propyl acetate, 16.6 parts tol
• a clear, curable, heat activatable adhesive layer is printed, consisting of 13.9 parts epoxy modified vinylchloride-vinylacetate copolymer resin (VERR, Union Carbide), 13.9 parts carboxyl modified vinylchloride-vinylacetate copolymer resin (VMCA, Union Carbide) dissolved in 34.6 parts ethyl acetate and 34.6 parts toluol, and containing 2.8 parts diglycidyl ether-bisphenol A epoxy resin (ERL-2774, Union Carbide) and 0.2 parts ultraviolet absorber (Uvinul D-SO, General Aniline and Film).
• VRR epoxy modified vinylchloride-vinylacetate copolymer resin
• VMCA carboxyl modified vinylchloride-vinylacetate copolymer resin
• the applied heatactivatable adhesive over-print was dried to a nontacky but heat-activatable state.
• the final print is monitored after the last press station under ultraviolet light which fluoresced the dye in the clear transfer layer (first down lacquer) to make it clearly visible, and was absorbed by the ultraviolet absorber in the overprinted clear adhesive layer (last down lacquer) so it appeared to be darker than the first down lacquer, whereby it is possible to keep the two clear lacquers and the ink print in perfect printing registration.
• the resulting decorative label is transferred to a glass bottle in the manner discussed above.
• an amino alkoxy silane i.e., a solution of gammaaminopropyltriethoxysilane (0.05% in Tolueneethanol) (A-l100, Union Carbide) is applied to the surface to be decorated.
• Application of the silane to the ware imparts significant hydrolytic resistance to the cured decoration on the ware.
• the container is then heated to -250F before the decoration is applied in a Dennison TDlB heat transfer decorating machine at a speed of about 60 bottles per minute.
• the decoration on the container is cured in an oven for 10 to 20 minutes at 200 to 300F and then further cured for 10 to 20 minutes in an oven at 350F to 450F.
• the lacquer layer which surrounds the ink print, and protects it, is observed to be water-white and nearly invisible.
• the cured decoration will withstand 40 rubs with methyl ethyl ketone with nothing removed, and a 30 minute immersion in boiling water with very little removed by scotch tape after cross-hatching with a razor.
• EXAMPLE 2 22.6 parts n-propyl acetate 11.0 parts toluol, 2.1 parts isopropanol, and containing 0.05 parts S-10 silicone resin. Titanium dioxide (OR-580, Cyanamid), 38 parts, is dispersed and ground into the above formulation as in Example 1. Printing, decorating and curing are the same as in Example 1.
• a reactive transparent blue ink may be printed in addition to and in line with the yellow ink in Example 1, over all of which a white ink may be printed as in Example 2.
• the reactive blue ink consists of 14.2 parts Resimene U-920, 10.8 parts VAGD, dissolved in 1 1.6 parts ethyl acetate, 31.9 parts n-propyl acetate, 15.5 parts toluol, 3.0 parts isopropanol, and containing 0.1 parts S-10.
• Monarch Blue pigment CFR X-3367 (Hercules), 12.9 parts is dispersed and ground into the above formulation as in Example 1. Printing, decorating, and curing are the same as in Example 1. The test results are also similar to those in Example 1.
• a reactive transparent red ink may be printed in addition to and in line with the yellow ink in Example 1, the blue ink in Example 3, over all of which a white ink may be printed as in Example 2.
• the reactive red ink consists of 14.5 parts Resimene U-920, 10.9 parts VAGD, dissolved in 1 1.9 parts ethyl acetate, 32.5 parts n-propyl acetate, 15.8 parts toluol, 3.1 parts isopropanol, and containing 0.1 parts S-10.
• Sparta Red pigment (Hercules), 10.9 parts, is dispersed and ground into the above formulation as in Example 1. Printing, decorating, and curing are the same as in Example 1, with similar test results.
• a stable heat transfer decoration comprising in combination a temporary carrier having a release surface from which the transfer is readily releaseable at elevated transfer temperature, and removably adhered to said surface in sequence a transfer lacquer layer, at least one design print layer, and a heat-activatable ad-' hesive layer, wherein at least said transfer lacquer and design print layers adjacent to and in contact with each other contain cross-linkable resin means for forming cross-linked polymers, at least one of said two adjacent layers containing cross-linking agent means for cross linking with said resin means in both layers, said agent means being stable at room temperature and activatable at elevated temperature to cross-link with said resin means within said one layer and between the two contacting layers, said resin and agent means being present in amounts effective to increase the abrasion and chemical resistance of the transfer decoration after application to a receiving surface and activation at elevated temperature.
• each of said layers contains cross-linkable resin means
• the transfer lacquer and heat-activatable adhesive layers each contain cross-linking agent means activatable to form cross-links at elevated temperature with the resin means in the design print layer.
• each of said layers contains cross-linkable resin means and cross-linking agent means activatable to form crosslinks within the layer and interlayer at the interface with the adjacent layer, whereby all layers are crosslinked together upon transfer and activation at elevated temperature.
• agent means are selected from the group consisting of blocked polyisocyanates, urea-formaldehyde resins and polyepoxide resins.
• cross-linkable resin means in the transfer lacquer layer is a cellulosic material containing sufficient hydroxyl substituents for cross-linking, and said transfer layer also contains a blocked polyisocyanate as said crosslinking agent means.
• the method of decorating a heat resistant surface of glass or metal comprising the steps of transferring to said surface from a release surface of a temporary carrier, under and heat and pressure, a decoration comprising in sequence a transfer lacquer layer, at least one design print layer, and a heat-activatable adhesive layer which is non-tacky at room temperature, wherein at least said transfer lacquer and design print layers adjacent to and in contact with each other contain crosslinkable resin means for forming cross-linked polymers, at least one of said two adjacent layers containing cross-linking agent means for cross-linking with said resin means in both layers, said agent means being stable at room temperature and activatable at elevated temperature to cross-link with said resin means within said one layer and between the two contacting layers, immediately stripping the temporary carrier from said layers, and curing said resin and agent means in said layers at a temperature between about 200F and about 450F to form a cross-linked structure within and between said layers, whereby an adherent cross-linked decoration is provided with improved resistance to abrasion and chemicals.
• each of said layers contains both said resin means and agent means and wherein said heat-resistant surface of said metal or glass is coated with primer means having cross-linkable substituents reactive at elevated temperature with the agent means in said adhesive layer, whereby all of said layers, after curing, are cross-linked together and to said primer.
• said primer is a silane
• said release surface is an inert thermoset resin
• said resin means in the transfer lacquer layer is a cellulose ester having sufficient hydroxyl substituents for cross-linking
• the agent means in said transfer layer is a blocked polyisocyanate
• said resin means in the design print layer has sufficient hydroxyl substituents for cross-linking
• said agents means in the design print layer is a urea-formaldehyde resin
• said resin means in the adhesive layer has sufficient hydroxyl or carboxyl substituents for cross-linking
• said agent means in the adhesive layer is a polyepoxide resin.
• a decorated article of glass or metal comprising primer means on a surface of said article and a heattransferred organic decoration comprising an adhesive layer over said primer means, at least one design print layer over said adhesive layer, and a protective transfer lacquer layer over said design print layer, all of said layers comprising polymeric resin means, all of said resin means and primer means being cross-linked intralayer and interlayer to form a unified adherent decoration resistant to abrasion and chemicals.
• said resin means in the adhesive layer has hydroxyl or carboxyl substituents cross-linked to said primer means by means of a polyepoxide resin.

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• Decoration By Transfer Pictures (AREA)

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Cited By (46)

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Citations (11)

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• 1973
  • 1973-11-08 US US41390873 patent/US3907974A/en not_active Expired - Lifetime
• 1974
  • 1974-11-06 AU AU75082/74A patent/AU497399B2/en not_active Expired
  • 1974-11-07 ES ES431739A patent/ES431739A1/es not_active Expired
  • 1974-11-07 CA CA213,229A patent/CA1034441A/en not_active Expired
  • 1974-11-07 ZA ZA00747160A patent/ZA747160B/xx unknown
  • 1974-11-07 DK DK580674AA patent/DK153676B/da unknown
  • 1974-11-07 SE SE7413978A patent/SE418595B/xx not_active IP Right Cessation
  • 1974-11-08 JP JP49128138A patent/JPS5920464B2/ja not_active Expired
  • 1974-11-08 BR BR941674A patent/BR7409416A/pt unknown
  • 1974-11-08 GB GB4847674A patent/GB1490703A/en not_active Expired
  • 1974-11-08 IT IT2924774A patent/IT1025545B/it active
  • 1974-11-08 FR FR7437206A patent/FR2250640B1/fr not_active Expired
  • 1974-11-08 NL NL7414610A patent/NL183507C/xx not_active IP Right Cessation
  • 1974-11-08 DE DE2453101A patent/DE2453101C2/de not_active Expired

Patent Citations (11)

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