MXPA01001702A - Glass decorating method using ink compositions containing n-vinyl lactams - Google Patents

Abstract

A method for decorating a vitreous substrate with a radiation curable ink composition, comprising applying an ink composition comprised of an N-vinyl lactam to the glass in a predetermined design, the ink being operable when cured to bond to the vitreous substrate, curing the ink on the vitreous substrate by exposing it to the radiation by which it is curable, thereby bonding the ink composition to the substrate;and a method for decorating a vitreous substrate with hot stamping foil comprising applying an ink composition comprised of an N-vinyl lactam to the glass in a predetermined design, the ink being operable when cured to bond to the vitreous substrate, curing the ink on the vitreous substrate by exposing it to the radiation by which it is curable, thereby bonding the ink composition to the substrate, pressing a sheet of hot stamping foil against the substrate with a die heated to a temperature sufficient to cause a portion of the hot stamping foil to adhere to the heated, cured, ink design but not to the ink free areas of the vitreous substrate, removing the die, thereby leaving behind a portion of the foil adhered to the ink design but not to the ink-free areas of the glass.

Description

METHOD FOR DECORATING GLASS USING INK COMPOSITIONS CONTAINING N-VINYL LACTAMAS TECHNICAL FIELD The invention is in the field of glass decoration with curable compositions with ultraviolet (UV) radiation.

BACKGROUND OF THE INVENTION Hot stamping is the heat transfer of a pigmented color or metallized surface of a polyester backing onto a thermoplastic substrate. A heated die or roll is used to apply pressure to the hot stamp sheet. The pressure forces the pigmented or metallized portion of the sheet into contact with the plastic substrate. The combination of heat and pressure softens the plastic substrate and activates the sheet, causing it to adhere to the substrate. A vertical stamping or roller machine is used for the operation. The vertical stamping machine contains a heated matrix of brass, steel or silicone rubber to transfer an area of a specific design as each part is placed in its position. The roller methods use a silicone rubber roll or arched die to apply the sheet in a continuous process or in batches. The heat transfer can be achieved at temperatures of approximately 107 ° C. Hot stamping is an efficient, cheap way to apply decoration to a thermoplastic substrate. Hot stamping can not be used in glass because the glass melts at a much higher temperature than other thermoplastic materials. Generally, decoration in the form of gold or silver foil, color designs or printing, is applied to a glass by a process similar to the glaze used with ceramics. Decoration with colored or metallic ink is applied to the glass container by a variety of methods such as silk screen, printing, etc. The container is then subjected to extremely high temperatures and the decoration is essentially baked. Unfortunately this process is time consuming, expensive, energy intensive and subject to safety considerations due to the high temperatures and gases needed to operate the kilns. The application of the hot stamped sheet to glass is described in U.S. Patent No. 5,708,047, which is incorporated herein by reference. First, the glass is printed with an epoxy ink, cycloaliphatic, radiation curable, and cured by exposure to radiation. The hot stamped sheet is applied and adheres to the cured ink design. However, the adhesion and durability of such decorated containers can always be improved. Accordingly, there is a need for ink compositions that provide improved adhesion and durability in the decoration of glass and other vitreous substrates.

SUMMARY OF THE INVENTION The invention comprises a method for decorating vitreous substrates with a radiation curable ink composition, comprising the steps of: a) applying an ink composition composed of N-vinyl lactam to the glass in a predetermined design , said ink being operable when cured to bind to the vitreous substrate, b) curing the ink on the vitreous substrate by exposing it to the radiation for which it is curable, thereby bonding the ink composition to the substrate, the invention further comprises a method for decorating glass substrates with hot embossing sheet comprising the steps of: a) applying an ink composition composed of an N-vinyl lactam to the glass in a predetermined design, said ink being operable when it is cured to bind to the vitreous substrate, b) the curing of the ink on the vitreous substrate by exposing it to the radiation by which it is emitted. s curable, therefore bonding the ink composition to the substrate, c) pressing a hot foil sheet against the substrate with a matrix heated to a temperature sufficient for a portion of the hot foil sheet to adhere to the design of the foil. hot cured ink but not to the ink-free areas of the vitreous substrate; d) removing the matrix, thereby leaving behind a portion of the sheet adhering to the ink design.

Detailed description All the percentages mentioned here are weight percentages, unless otherwise indicated.

INK COMPOSITIONS USED IN THE N-VINYL LABAMATE METHOD The ink compositions used in the method of the invention contain 10-60%, preferably 15-55%, more preferably 20-50% of an N-vinyl lactam.

Preferably the N-vinyl lactam comprises a lactam having 4 to 6 carbon atoms in the ring. The N-vinyl lactam may be solid or liquid at room temperature, and is a monomer, oligomer or homo or copolymer of low molecular weight. Preferably, the N-vinyl lactam has a molecular weight of from about 100 to about 150 daltons. The preferred N-vinyl lactams for use in the method of the invention are N-vinyl pyrrolidone and N-vinyl caprolactam. N-vinyl pyrrolidone can be purchased from International Specialty Products, Wayne, New Jersey, and has CAS Registry No. 86-12-0. This monomer has a molecular weight of 111 daltons v is a liquid at room temperature, and has a melting point of 17 ° C. N-vinyl caprolactam can also be purchased from International Specialty Products, and has CAS Registry No. 2235-00-9. This monomer has; a molecular weight of 139 daltons and is a solid at room temperature, has a melting point of 35 ° C. In the preferred embodiment of the invention, the ink composition contains N-vinyl caprolactam.

Other ethylenically unsaturated monomers or oligomers Preferably, the ink compositions also contain other ingredients such as one or more ethylenically unsaturated oligomers or monomers in addition to N-vinyl lactam. A variety of other oligomers or ethylenically unsaturated monomers can be used, including all those cured by free radicals and by cationic mechanisms. Preferably, the ink compositions contain 15-65%, preferably 20-60%, more preferably 25-50% by weight of the total composition of at least one monomer, ethylenically unsaturated oligomer, or homo or copolymer of low molecular weight in addition to the N-vinyl lactam. Suitable monomers may contain free acid groups, such as a carboxylic acid group, sulfonic acid or phosphoric acid. The phrase "having a free acid group" means that the monomer unit has at least one free acid group, or the oligomer contains at least one monomer unit that contains a free acid group or is a homo- or copolymer, at least a monomeric unit thereof contains at least one free acid group. Preferably, the ink composition contains a monomer or oligomer, in particular an ethylenically unsaturated monomer or oligomer having at least one free acid group. Examples of preferred monomers or oligomers include all those having carboxylic acid functional groups such as: I.

, 'CH2 = C COOH wherein Rx is H, an unsubstituted or substituted, saturated or unsaturated, straight or branched C 1 -C 3 alkyl, aryl, aralkyl, a pyrrolidone, or a substituted or unsubstituted alicyclic or bicyclic aromatic ring, wherein the substituents are straight or branched chain alkyl of C? -3o or halogen. Also suitable are the ethylenically unsaturated monomers or oligomers having the unit formula: II COOR2 wherein Ri is as defined above, and R2 is an alkyl, aryl, aralkyl of C? _30, straight or branched chain, substituted or unsubstituted, saturated or unsaturated, a pyrrolidone, or an aromatic alicyclic ring or substituted or unsubstituted bicyclic, wherein the substituents are straight or branched chain alkyl of C? -30 or halogen; or 2-tetrahydrofuran; or X-COOH wherein X is an alkyl, aryl or arylalkyl of C? -30, straight or branched chain or (CH2CH2-0) nY COOH or (CH2CH2CH2-0) nY COOH wherein Y is a straight-chain alkyl or branched from C? _ 10 and n is 1-10,000. Preferably the monomer or oligomer is of formula II, wherein Ri is H or CH3, and R2 is 2-tetrahydrofuran or X-COOH wherein X is a straight or branched chain alkyl of Ci-io, more preferably ethyl. More preferably, the composition comprises a mixture of morimomers or oligomers of the formula II, the first being wherein R2 is 2-tetrahydrofuran, and the monomer or oligomer is tetrahydrofurfuryl acrylate, which preferably has a molecular weight of about 156 daltons and is a clear liquid that have a specific gravity of approximately 0.872. This tetrahydrofururyl acrylate is sold by the Sartomer Company under the trademark SR 285. The second preferred monomer or oligomer of the formula II is where R2 is also betacarboxyethyl, for example, beta-carboxyethyl acrylate, which is sold under the trademark B -CEA by UCB Radcure, Inc. B-CEA is a reactive monomer containing both functionalities, acrylate and carboxylic acid, predominantly as the dimer acrylic acid, and in particular, a mixture of approximately 40% by weight B-carboxyethyl acrylate, approximately 40% by weight. % by weight of higher homologs of acrylic acid and about 20% by weight of acrylic acid. The B-carboxyethyl acrylate component of this mixture has the following formula: In addition, the ink composition may also contain oligomers with carboxylic acid functional such as semi esters of aromatic acid methacrylate and aromatic acid acrylate half esters, monomers with functional acid are also suitable for use in the method of the invention. Examples of such oligomers are partial esters of anhydride-containing polymers such as those described in U.S. Patent No. 4,722,947 which is incorporated by reference. These copolymers correspond to the following formula: wherein Ri and R2 are each independently hydrogen, C? _20 alkyl, aryl, alkaryl, cycloalkyl or halogen; R3, R4 and R5 (see below) are each independently hydrogen, C2-2alkyl or aryl; and R6 is the same or different and is alkyl, aralkyl or an aralkyl radical substituted with alkyl containing about 1 to 20 carbon atoms, as well as oxyalkylated derivatives thereof; and the subscripts x, y, z and p are each integers such that the sum of x, y, z and p can vary from about 3 to 20; and x, p and y are each equal to or greater than '.., and z can be 0; and B is -OAOCOCR5CH2, wherein A is a linear or branched divalent alkylene, from about 1 to 20 carbon atoms, or an oxyalkylated derivative thereof, as described for R6. The copolymers containing partial esters of particularly preferred anhydrotic anhydrides are those expired by Sartomer Inc. under the trademark Sarbox, such as SB-400, SB-500 and SB-600. Particularly preferred is the aromatic acid methacrylate half ester of trimethylolpropane ethoxylate triacrylate which is sold by Sartomer Inc. under the trademark Sarbox SB500E50. Other monomers with functional carboxylic acid include acrylic acid, bisacrylamidoacetic acid, 4-bis (4-hydroxyphenyl) pentanoic acid, 3-buten-1,2,3-tricarboxylic acid, 2-carboxyethyl acrylate, itaconic acid, methacrylic acid, 4-vinylbenzoic and mixtures of these materials. Examples of monomers containing sulfonic acid groups include 2-acrylamido-2-methyl-l-propanesulfonic acid; 2-methyl-2-propene-1-sulphonic acid, 2-propene-1-sulfonic acid, 4-styrenesulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyldimethyl-3-methacrylamidopropyl ammonium inner salt, 3-sulfopropylmethacrylate, vinylsulfonic acid and so on. Examples of monomers containing functional phosphoric acid groups include bis (2-methacryloxyethyl) phosphate, monoacryloxyethyl phosphate, and so on. Other monomers, oligomers or homo, or low molecular weight copolymers, terpolymers or block copolymers, or grafted, radiation curable which do not contain free acid groups are also suitable. Examples of suitable monomers include epoxides, cycloaliphatic epoxides, vinyl chloride, styrene, ethyl acrylate, vinyl acetate, difunctional acrylic monomers such as hydroxyalkyl acrylates or hydroxyalkyl methacrylates, vinyl butyrate, vinyl methyl ether, methyl methacrylate, isobornyl acrylate, acrylonitrile or mixtures thereof. Suitable polymers include oligomers, homo- or copolymers, terpolymers or grafted copolymers of the above monomers provided they have a molecular weight of less than about 50,000, otherwise it is very difficult to effect polymerization, ie curing. Preferred are acrylate homopolymers or methacrylate or acrylate copolymers, preferably acrylate or acrylate copolymers Examples of such acrylate or methacrylate copolymers include epoxy acrylates, copolymers of propylene glycol and a dicarboxylic acid, urethane acrylates and the like. , the compositions contain one or more polymerizable reactants, selected from the group consisting of: urethane acrylate, tripropylene glycol acrylate, epoxy acrylate copolymers and mixtures thereof.

Pigment The compositions used in the invention may contain 5-95%, preferably 5-50%, more preferably 8-35% by weight of the total pigment composition. A wide variety of pigments are suitable, including organic and inorganic pigments. Examples of these pigments are stated in U.S. Patent No. 5,178,952, which is incorporated herein by reference. Inorganic pigments include spreading pigments such as barite, barium sulfate, calcium carbonate, talc, clay, alumina, titanium dioxide, white carbon, china white, zinc sulphide, lithopone, ultramarine, Prussian blue, cobalt, chrome oxide, viridian chrome green, yellow, orange and red, cadmium, chromium, iron oxides, carbon black, metallic pigments, aluminum powder, bronze powder, zinc chromate, strontium chromate, zinc powder, copper and so on. Examples of suitable organic pigments include azo pigments, indolinones, isoindolinones, tub pigments, lacquers, phthalocyanine pigments and so on. The preferred pigment for imparting the white color to the ink composition is titanium dioxide. The yellow and red pigments are isoindolinones and pyrrolopyrroles as described in U.S. Patent Nos. 4,415,685; 4,579,949; 4,791,204; 4,666,455; 5,074,918; 4,783,540; 4,914,211; 4,585,878; as well as U.S. Patent No. No. [sic] 5,571,359 to Kamen et al., all of which are incorporated herein by reference. These pyrrolopyrroles are generally of the formula: wherein Ri and R2 are each independently alkyl, arylalkyl, eryl, substituted or unsubstituted heterocyclic or isocyclic aromatic radicals, R3 and R are each independently H, substituted or unsubstituted alkyl, alkoxycarbonyl, aroyl (eg benzoyl) , arylalkyl (for example benzyl), aryl (for example phenyl), alkanoyl, C5_6 cycloalkyl, alkenyl, alkynyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl or alkoxycarbonyl; and X is O or S. The preferred compound is one wherein R x and R 2 are each independently phenyl or naphthyl, R 3 and R 4 are hydrogen, and X is O. A particularly preferred red pigment is pyrrolo 3, 4-C pyrrol-1. , 4-dione, 2,5-dihydro-3,6-di-4-chlorophenyl having a CAS number 84632-65-5 and is known by the common name CI red pigment 254. This pigment is commercially available from Ciba- Geigy Pigments Division, Newport, DE, under the trademark Irgazin DPP Red 80. Other red Ciba-Geigy pigments sold under the trademark Irgazin are also suitable.

Suitable isoindolinones are as disclosed in U.S. Patent Nos. 3,884,955, 3,867,404, 4,978,768, 4,400,507, 3,897,439 and 4,262,120 and 5,194,088 all of which are incorporated herein by reference. Preferred isoindolinones are alkyl esters of tetrachlorocyanobenzoic acid, particularly benzoic acid, 2, 3, 4, 5-tetrachloro-6-cyanomethyl ester which is reacted with 2-methyl-1,3-benzenediamine and sodium methoxide. The composition of this pigment has the common name Pigment C. I. yellow 109 and is commercially available from Ciba-Geigy division pigments, Newport DE under the trademark Irgazin yellow 2GLTE. Other pigments are also suitable in the yellow Irgazin series thus manufactured by Ciba-Geigy. Particularly suitable blue pellets are marketed by Ciba-Geigy under the trademark Blue Irgazin X-3367 or by Whittaker, Clark & Daniels under the ultramarine blue registered trademark 5009.

Defoaming or surfactant agent The ink compositions used in the invention also preferably contain about 0.01-10% of a defoaming or surfactant agent. Defoaming agents cause smooth surfaces by applying the ink on the glass substrate without bubbles or roughness.

A wide variety of defoamers are suitable, such as the polyether defoaming agents sold by BYK Chemie under the trademark BYK. Examples of such defoaming agents are alkyl vinyl ether polymers disclosed in U.S. Patent No. 5,187,201, which is incorporated herein by reference. Examples of other defoamers include polyethers such as BYK-052, BYK-053 and BYK-033. BYK-052 and -053 are polyethers such as polyethylene or polypropylene glycol ethers, and in particular polyvinyl ethers. Also suitable are BYK-354 which is a solution of polyacrylate and BYK-022 which is a mixture of hydrophobic solids polysiloxane foam-destroying polyglycol. Preferably, the polyether defoaming agent is an alkoxylated alkyl phenol, more particularly a mixture of petroleum distillates and an ethoxylated alkyl phenol, such as sold by BYK-Chemie under the trademark BYK-033. Also suitable are some surfactants which may be cationic, anionic, amphoteric, zwitterionic or non-ionic. Suitable amphoteric surfactants are generally derived from aliphatic secondary or tertiary amines wherein one aliphatic radical is a straight or branched alkyl chain of 8 to 18 carbon atoms and the other aliphatic radical contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. Suitable zwitterionic surfactants include betaines, as well as those of the general formula: R2-Y-CH2-R4-Z " wherein R2 contains an alkyl, alkenyl or hydroxyalkyl radical of from about 8 to 18 carbon atoms, from 0 to about 10 ethylene oxide fractions and 0 or 1 glyceryl fraction; And it is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom, and 2 when Y e; s a nitrogen or phosphorus atom; R 4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups. Suitable anionic surfactants include alkyl ether sulphates and sulphonates, as well as olefin succinates, succinmates and sulfonates. Preferably, the surfactant is a nonionic surfactant. Nonionic surfactants are generally compounds produced by the condensation of alkylene oxide groups with a hydrophobic compound. The classes of ro ionic surfactants are: (a) Long chain dialkyl sulfoxides containing an alkyl or short chain hydroxyalkyl radical of from about 1 to 3 carbon atoms and a long hydrophobic chain which may be an alkyl, alkenyl, hydroxyalkyl or ketoalkyl containing from about 8 to 20 carbon atoms, from 0 to 10 portions of ethylene oxide and 0 or a glyceryl fraction. (b) Polysorbates, such as sucrose esters of fatty acids. Examples of such materials include sucrose cocoate, sucrose behenate and so forth. (c) Polyethylene oxide condensates of alkyl phenols, for example the condensation products of alkyl phenols having an alkyl group of 6 to 20 carbon atoms with ethylene oxide being present in amounts of about 10 to 60 moles of ethylene per mole of alkyl phenol. (d) Condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine. (e) Condensation products of aliphatic alcohols having from 8 to 18 carbon atoms with ethylene oxide, for example, a condensate of coconut alcohol / ethylene oxide having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the fraction of coconut alcohol has 10 to 14 carbon atoms. (f) Long chain tertiary amine oxides such as those corresponding to the general formula: R? R2R3NO wherein Ri contains an alkyl, alkenyl or monohydroxyalcryl radical ranging from about 8 to about 18 carbon atoms long, 0 up to 10 fractions of ethylene oxide and from 0 to about a glyceryl fraction and R2 and R3 are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. (g) Long chain tertiary phosphine oxides corresponding to. the general formula: RR? R2PO wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical having 8 to 18 carbon atoms, and from 0-10 ethylene oxide fractions and 0 or 1 glyceryl fraction, and R2 and R3 are each an alkyl or monohydroxyalkyl group containing from about 1 to 3 carbon atoms. (h) Alkyl polysaccharides having a hydrophobic group of 6 to 30, preferably 10 carbon atoms and a polysaccharide group such as glucose, galactose, etc. Suitable alkyl polysaccharides are octyl, nonidecyl, undecyldecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides; galactosides, lactosides, glucoses, fructosides, fructose and so on, (i) Polyethylene glycol (PEG) glyceryl fatty esters, which are the reaction products of polyethylene glycol, glycerin, and fatty acids. Suitable PEG glyceryl fatty esters can be monoesters, diesters or triesters. Such compounds are manufactured by Goldschmidt Corporation under the trademark TAGAT. Suitable monomers include, for example, those having the general formula: RC (O) OCH2CH (OH) CH2 (OCH2CH2) nOH wherein n is 2-200 and RC (O) - is a hydrocarbylcarbonyl group, wherein R is an aliphatic radical having 7 to 30, preferably 8-20 atoms carbon. (j) Other nonionic non-ionic surfactants that may be used include C 1-4 alkyl polyhydroxy (Ci-e) fatty acid amides such as C 12-18 methyl glucamides, fatty acid N-alkoxy polyhydric oxide, N-hexyl propyl glycoimides of C? 2_? 8, and so on. Other suitable nonionic surfactants include fluorinated nonionic surfactants. The term "surfactant: or fluorinated ion" means a fluorine-containing compound having at least one lipophilic moiety or group and at least one hydrophilic moiety or moiety. Examples of such surfactants are those disclosed in U.S. Patent No. 4,961,976 which is incorporated herein by reference. Also suitable are fluorocarbon surfactants, such as those commercially available under the trademark Fluorad by 3M Company. These fluorochemical surfactants include fluorinated alkyl esters, fluorinated alkyl polyoxyethylene ethanol, and the like. The fluorinated alkyl alkoxyalkylates are commercially available from 3M under the trademark FC-171. Preferred nonionic surfactants for use in the present invention are glyceryl polyethylene glycol fatty esters of the formula: RC (O) OCH2CH (OH) CH2 (OCH2CH2) nOH wherein n is 2-200 and RC (O) - is a hydrocarbylcarbonyl group, wherein R is an aliphatic radical having 8-20 carbon atoms. Particularly preferred is a fatty acid monoester of glyceryl polyethylene glycol sold by Goldschmidt Corporation under the trademark Tagat S5, which is PEG-5 glycerylmonostearate. In the preferred embodiment of the invention, Tegoglas T5 is used, which is an aqueous solution of Tagat S5, sold by Goldschmidt Corporation.

Adhesion Promoter The ink compositions used in the invention also preferably contain about 0.01-25%, preferably from 0.05-15%, more preferably about 0.1-5% of a silane adhesion promoter which will improve the adhesion of the cured resin on the vitrea surface. Examples of silanes are silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, amino silanes or isocyanoto silanes [sic]. Suitable silanes include organofunctional silanes of the formula: Y- (CH -SiX ^ <CH3) a wherein: n = 0-3 a = 0-2 Y = NH2, CHj = CH, CH2 = C- C0O- CH3-NH-, NH2-C0-NH-, HS-. CI-Nl-yCHüfeNH-, CH3 X is each independently CH3, Cl, 0C0CH3, 0C2H40CH3 (0C2H4; 2OCH3 or -OR, wherein R is a straight or branched chain alkyl of C? -2o, preferably methyl or ethylc.Silanes having this formula are available ocially under the Dynasylan trademark of Huís, America, Inc., Piscataway, New Jersey or Osi Specialties Inc. Other organofunctional silanes such as those described in U.S. Patent No. 5,221,560, which is incorporated herein, are also suitable . Such organosilanes are silanes acriloxifuncionales including 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-metacriloxietiltrimetoxisilano, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 2-metacriloxieítiltrietoxisilano, 2-metacriloxie: tiltrietoxisilano, 3-acryloxyethyltriethoxysilane, etc. The glycidoxysilane Suitable examples include: 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxyeti -triethoxysilane, 3-glycidoxypropyltrimethylsilane, and so on. Preferred for use in the compositions of the invention are silanes with acryloxy function, isocyanate silanes, and aminosilanes. The silane with preferred acryloxy function is 3-methacryloxypropyltrimethoxysilane, sold by Huís America, Inc., under the trademark DYNASYLAN MEMO. The preferred amino silane is sold by Huís America with the brand DDYNASYLAN TRIAMO. The preferred isocyanate silane is sold by Osi Specialties Inc., under the registered trademark A-1310. In the preferred ink compositions of the invention, a mixture of three silanes, generally 0.01-2% by weight each, is preferred.

Photoinitiator The ink compositions preferably contain an initiator photo which catalyzes the polymerization of the monomers upon exposure of the radiation by means of which the monomers are curable. These are generally two types of photoinitiators: free radicals and cationic. Free radical initiators are most commonly used with ethylenically unsaturated monomers and oligomers, while cationic photoinitiators are used with epoxy or vinyl ether functional resins. Preferably, the compositions in the invention contain photo initiators by free radicals. Suitable free radical type photoinitiators include carbonyls such as ketones, acetophenones, benzophenones, derivatives thereof. Examples of such materials constitute, for example, methyl ethyl ketone; benzophenone, benzyl dimethyl ketal; 1-hydroxycyclohexylphenyl ketone; dietioxycetophenone; 2-methyl-1- (methylethiophenyl) -2- (4-morpholinyl) -1-propanone [sic]; 2-benzyl-2-N, N-dimethylamino-1,4- (4-morpholinophenyl) -1-butanone; 2, 2-dimethoxy-2-phenyl acetophenone; 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-hydroxy-2-methyl-1-phenyl-propan-l-one; 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-methylpropyl) ketone; and mixtures of bis (2,6-dimethoxybenzoyl) -2-4-4-trimethylpentyl phosphine of oxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one. Preferably it is 2-methyl-1- (methylthiophenyl) -2- (4-morpholinyl) -1-propanone a mixture of 25% bis- (2,6-dimethoxybenzoyl) -2-4-4-trimethylpentyl phosphine and oxide and 75% 2-hydroxy-2-methyl-1-phenyl-propan-1-one, which are sold under the trademark Irgacure 907 and Irgacure 1800 from Ciba-Geigy.

The cationically curable monomers or oligomers can be used in the compositions of the invention. Examples of cationically curable monomers or oligomers include those with epoxy or epoxide groups, such as cyclic aliphatic epoxides as disclosed in U.S. Patent No. 5,708,047 or bisphenol-A epoxy resins published in U.S. Patent No. 5,656,336, both of which are incorporated as reference. If the cationically curable monomers or oligomers are used in the ink compositions, it is desirable to use cationic photoinitiators. The term "cationic photoinitiator" means a molecule or ingredient that, by excitation, undergoes a photochemical transformation that efficiently generates a species capable of initiating cationic polymerization. If the ink composition of the invention is cured by UV or actinic radiation instead of an electron beam, it is desirable to add a cationic photoinitiator that catalyzes the crosslinking of the resin by exposure to the radiation to which the resin is sensitive. On the other hand, if the ink compositions of the invention are cured with electronic beam it may be possible to omit with the cationic photoinitiator. Several types of cationic photoinitiators are suitable. Both ionic cationic photoinitiators, such as onium salts or organometallic salts, are also suitable as well as other cationic nonionic initiators such as organosilanes, latent sulfonic acids and the like. Sensitive onium salts are preferred, in particular onium salts such as those published in U.S. Patent Nos. 4,058,401, 4,138,255, 4,161,478, 4,175,972 all of which are incorporated by reference. More preferred are triaryl sulfonium salts, in particular triaryl sulfonium salts such as those sold by Union Carbide under the trademark Cyracure UVI6990 and 6974. Also suitable are ferrocenium salts such as those sold under the trademark Irgacure by Ciba- Geigy, particularly Irgacure 261. Sulfonyloxy ketones and silyl benzyl ethers are also good photoinitiators; s cationic. A detailed analysis of the mechanism of cationic curing is published in "Photosensitized Epoxides as a Basis for Light-Curable Coatings" by William R. Watt, American Chemical Society, Symposium, Ser. 114, Epoxy Resin Chemistry, Chapter 2, 1979, and in "Chemistry and Technology of UV and EB Formulation for Coatings, Inks, and Paints", Volume 3, entitled "Ph? 7? Initiators for Free Radical and Cationic Polymerizatiop, KK Dietliker, pages 332-374 (1991), both of which are incorporated herein by reference Lais photosensitive onium salts are used as photoinitiators in cationic curing, in particular, onium salts such as those published in US Patent Nos. 4,058,401, 4,138,255, 4,161,468, 4,175,972, all of which are incorporated herein by reference.For cationically curable monomers or oligomers triaryl sulfonium salts are more preferred, in particular triarylsulfonium salts such as those sold by Unió Carbide under the trademark Cyracure UVI6990 and 6974. The photoinitiator is generally present at about 0.1-15%, preferably from about 0.5-12%, more preferably from about 0.5-10% by weight of the total composition.

Preferred ink compositions used in the method of the invention comprise: -50% of an N-vinyl lactam, 10-65% of an ethylenically unsaturated monomer or oligomer in addition to the N-vinyl lactam, 0.01-10% of a non-ionic surfactant.

THE METHOD The term "matrix" means any object that is capable of being heated to a temperature sufficient to cause hot stamping of a sheet to adhere to the cured ink design, and is capable of compressing the hot stamping sheet against the substrate. . Suitable matrices include matrices of brass, steel, or silicone rubber found in traditional stamping machines, manual rollers, silicone rubber rollers, arched matrices, and so on.

The term "substrate" means glass, ceramic or other similar vitreous substrates which are amenable to decoration including containers, decorative objects, figurines, glasses, windows, tiles and others.

The term "hot foil sheet" generally means a laminate composed of a carrier material (often polyester, cellulose acetate, or other similar material capable of being separated), a separable film, and a decorative or colored cover , in that order. The decorative cover is usually colored or metallized cover. The metallized cover can be real gold or silver, or aluminum, which is colored to look like gold or silver, or has holographic properties. The colored layer is most often applied by vacuum metallization. More specifically, the hot embossing sheet can be defined as a multilayer fabric composed of a reinforcing film carrier, a separable cover, one or more protective top covers, and one or more color covers, and an adhesive that is It melts hot, in that order. In the general hot stamping process, the hot melt adhesive layer of the sheet is pressed against the substrate with a heated matrix. The hot melt adhesive layer adheres to the substrate and the application of heat also causes the layer to separate to release the carrier from the reinforcing film of the upper protective layer of the cover leaving the upper protective layer of the cover exposed. on the surface of the substrate. The release cover is any wax or wax-like material, or a thermoplastic material that is melted by the application of heat to release the top protective layer from the carrier cover of the reinforcing film. Suitable thermoplastics used for separable layers include ethylene vinyl acetate, (EVA), acrylics, polyvinyl chlorides (PVC), polyamides, or similar thermoplastic materials as disclosed in U.S. Patent No. 5,104,719, which is incorporated herein by reference. reference. The protective top cover is usually a lacquer or some type that is capable of protecting the colored or metallized layer. The final layer is a hot melt adhesive, which can be a wide variety of substances and is selected to be capable, by the application of heat, of adhering to the substrate to which it is applied. Generally thermoplastic materials such as EVA, and PVC and the like are suitable for hot melt.

The term "actinic radiation" means light having a wavelength of 4 to 600 nm.

The term "ultraviolet radiation" or "UV" means light having a wavelength of 4 to 400, preferably 325 to 365 nm.

The method of the invention comprises the decoration of vitreous substrates such as glass, tile, ceramic products, and the like with hot stamping foil. The ink composition can be applied to the vitreous substrate in a variety of ways including silk stenciling, or screen printing, offset printing, to any other application technique. Stencil silk is preferred because it is adaptable to online production. Manual application using paint brushes or other similar hand-aid applicators may be employed where the ink is applied to a substrate such as a figure or other highly decorative article that is not very susceptible to stencil printing.

After the ink composition is applied to the substrate, it is cured by exposure to radiation, whereby it is curable. The electron beam can be used to cure the ink, although actinic radiation is used, preferably ultraviolet (UV) radiation. The ink on the decorated substrate is cured by exposure to UV light for a period of time to effect the polymerization of the monomers present in the ink, usually varying from fractions of one second to about 3 minutes, depending on the thickness of the applied ink to the substrate. UV conveyors like those made by Fusion Systems work well for this purpose. UV transporters are composed of a tradisporting band located under a UV lamp. When the substrate is placed on the conveyor belt, it moves along and is irradiated by the lamp. Of course, when curing times are longer, the substrate can suddenly pass through several conveyors in line, or several times through the same conveyor. The conveyor apparatus is set so that the ink passes through for the appropriate amount of time to cure and adhere to the substrate.

After the ink has been cured and adhered to the substrate and provides decorative, durable signs.

It may be desirable to apply the hot stamp sheet to the cured ink design. If so, the substrate is stamped with the hot stamping foil. In particular, the sheet is pressed against the substrate with a hot matrix for a sufficient amount of time to cause the hot stamping sheet to adhere to the cured ink pattern but not to the ink-free areas of the glass. Generally, the matrix should be heated to a temperature of 250 to 400 ° F (121 ° C to 204 ° C), preferably 250 to 350 ° F (121 ° C to 177 ° C) to cause adhesion of the sheet to the design of t.inta cured. The matrix is compressed against the substrate for a period of time ranging from fractions of one second to several minutes depending on the matrix used, the temperature of the matrix of the matrix and the composition of the ink. When the heated matrix is removed, the hot stamping foil is removed immediately. A portion of the hot stamping foil, in particular the hot melt adhesive layer and the colored or metallized layer, and the upper protective cover, if present, in that order, remain fixed to the cured ink design. so that the hot melt adhesive adheres to the cured ink design, followed by the colored cover layers, and the top protective uncoated layer on the surface of the container. The upper protective cover may or may not contain part of the covering layer that comes off, which is designed to detach the colored layer from the protective top cover.

The decoration applied to the substrate by this method is extremely durable and capable of withstanding the severe conditions necessary to make it commercially acceptable.

The invention will be further described in relation to the following examples which is established for the purposes of illustration only.

EXAMPLE 1 The ink composition was made as follows: 1 V-Cap / RC, CAS Reg. No. 2235-00-9, International Specialty Products, Wayne, New Jersey. 2 Celluous acetate butyrate, CAS Reg. No. 009004-36-8, Eastman Chemical Company, Kingsport, TN. 3 SR285, Sartomer Company Inc. 4 B-CEA, UCB Radcure Inc.

A 50:50 mixture of bis- (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide and 1-hydroxycyclohexyl phenyl ketone, Ciba-Geigy Corp. 6 2-methyl-1- [4- (methylthio ) phenyl] -2-morpholino propan-1-one 7 Polydimethylsiloxane dispersed in silicic acid, Goldschmidt Corporation, Hopewell, GOES. . 8 Gamma-isocyanatopropyltriethoxysilane A-1310, Osi Specialties Inc. 9 DYNASYLAN MEMO, Huís America Inc. (Sivento) 10 CN104, Sartomer Company n Semi-ester of aromatic methacrylic acid in ethoxylated trimethylolpropane triacrylate, Sartomer Company The ink composition was made by combining the ingredients and was mixed.

EXAMPLE 2 The ink composition of Example 1 was sieved in a glass cosmetic container using a silk stencil having 220 mesh. The ink was cured by exposure to UV radiation. The ink adhered well to the resulting decorated container.

EXAMPLE 3 The hot embossing sheet was applied to a decorated container according to Example 2. The hot embossing sheet was applied to the cured, heated design by compressing the sheet against the ink with a hot compress. The hot stamp sheet adhered to the cured ink design but not to the ink free glass areas.

Although the invention has been described in relation to the preferred embodiment, it is not intended to limit the scope of the invention to the particular form presented but, on the contrary, is proposed to cover such alternations, modifications, and equivalents as may be included within the spirit and scope of the invention, as defined by the attached clauses.

Claims (20)

2. A method for decorating a vitreous substrate, comprising the steps of: a) applying an ink composition composed of an N-vinyl lactam to the glass in a predetermined design, said ink being operable when cured to bind to the vitreous substrate. b) curing the ink on the vitreous substrate by exposing it to the radiation by means of which it is curable, thereby bonding the ink composition to the substrate.
3. The method of claim 1, wherein the N-vinyl lactam consists of a lactam having 4 to 6 carbon atoms.
4. The method of claim 2, wherein the N-vinyl lactam has a molecular weight of 100-150.
5. The method of claim 3, wherein the N-vinyl lactam is selected from the group consisting of N-vinylpyrrolidone, -vinyl caprolactam, and mixtures thereof.
6. The method of claim 4, wherein the N-vinyl lactam is a solid at room temperature.
7. The method of claim 5, wherein the N-vinyl lactam is N-caprolactam.
8. The method of claim 1, wherein the ink composition is curable by exposure to ultraviolet radiation.
9. The method of claim 1, wherein the ink composition comprises, by weight of the total composition: 20-50% N-vinyl lactam 10-60% of a second ethylenically unsaturated monomer or oligomer in addition to the N-vinyl lactam, and 0.01-10% of a non-ionic surfactant.
10. The method of claim 8, wherein the second ethylenically unsaturated monomer or oligomer is selected from the group consisting of:
11. I. wherein Ri is H, an alkyl, aryl, Ci-30 aralkyl, straight or branched chain, substituted or unsubstituted, saturated or unsaturated, a pyrrolidone, or an unsubstituted or substituted, aromatic, alicyclic or bicyclic ring. , wherein the substituents are C-30 alkyl, straight or branched chain or halogen.
12. II
13. CH »-C I
14. COOR2 wherein Ri is as defined above, and R2 is an alkyl, aryl, C? _30 aralkyl, straight or branched chain, unsubstituted or substituted, saturated or unsaturated, a pyrrolidone, or an aromatic, alicyclic ring or substituted or unsubstituted bicyclic, wherein the substituents are C?-30 alkyl, straight or branched chain or halogen; or 2-tetrahydrofuran; or X-COOH wherein X is an alkyl, aryl or arylalkyl of C3_3, straight chain or branched chain or (CH2CH2-0) nY COOH or (CH2CH2CH2-0) nY COOH, wherein Y is an alkyl of Ci-io , linear or branched chain and n is 1-10,000; and III. wherein Ri and R2 are each independently hydrogen, C2_2alkyl, aryl, alkaryl, cycloalkyl or halogen; R3, R4 and R5 (see below) are each independently hydrogen, Ci-20 alkyl or aryl; and R6 is the same or different and is alkyl, aralkyl or an aralkyl radical substituted with alkyl containing about 1 to 20 carbon atoms, as well as oxyalkylated derivatives thereof; and the subscripts x, y, z and p are each integers such that the sum of x, y, z and p can vary from about 3 to 20; and x, p and y are each equal to or greater than 1, and z can be 0; and B is -OAOCOCR5CH2, wherein A is a linear or branched divalent alkylene, from about 1 to 20 carbon atoms, or an oxyalkylated derivative thereof, as described for R6. The method of claim 8, wherein the nonionic surfactant is a glyceryl polyethylene glycol fatty ester of the formula
15. RC (0) OCH2CH (OH) CH2 (OCH2CH2) nOH wherein n is 2-200 and "RC" (O) - is a hydrocarbylcarbonyl group, wherein R is an aliphatic radical having 8-20 carbon atoms.
16. A method for decorating a vitreous substrate with hot foil sheet comprising the steps of: a) applying an ink composition composed of an N-vinyl lactam to the glass in a predetermined design, said ink being operable when cured to bind to the vitreous substrate. b) curing the ink in the vitreous substrate by exposing it to the radiation by means of which it is curable, thereby bonding the ink composition to the substrate, c) 'compressing a hot foil sheet sheet against the substrate, with a matrix heated to a temperature sufficient to cause a portion of the hot foil sheet to adhere to the heated ink design, cured but not to the areas free of vitreous substrate ink. d) remove the matrix, with this leaving behind a portion of the sheet adhered to the ink design.
17. The method of claim 11, wherein the N-vinyl lactam consists of a lactam having 6 carbon atoms in the ring.
18. The method of claim 12, wherein the N-vinyl lactam has a molecular weight of 100-150.
19. The method of claim 12, wherein the N-vinyl lactam is selected from the group consisting of N-vinyl pyrrolidone, -vinyl caprolactam, and mixtures thereof. 15. The method of claim 14, wherein the N-vinyl lactam is a solid at room temperature. 16. The method of claim 14, wherein the N-vinyl lactam is N-vinyl caprolactam. 17. The method of claim 11, wherein the ink composition is curable by exposure to ultraviolet radiation. 18. The method of claim 11, wherein the ink composition comprises:
20. 20-50% N-vinyl lactam 10-60% of a second monomer or ethylenically unsaturated oligomer in addition to the N-vinyl lactam, and 0.01-10% of a non-ionic surfactant. 19. The method of claim 18, wherein the second ethylenically unsaturated monomer or oligomer is selected from the group consisting of: CH2 = C COOH wherein Ri is H, an alkyl, aryl, aralkyl of C? _ 30, linear or branched chain, substituted or unsubstituted, saturated or unsaturated, a pyrrolidone, or an aromatic ring, substituted or unsubstituted alicyclic or bicyclic, wherein the substituents are C1-30 alkyl, straight or branched chain or halogen. II wherein Ri is as defined above, and R2 is an alkyl, aryl, C? -30 aralkyl, straight or branched chain, substituted or unsubstituted, saturated or unsaturated, a pyrrolidone, or an aromatic ring, substituted or unsubstituted alicyclic or bicyclic, wherein the substituents are C 1 -3 alkyl, straight or branched chain or halogen; or 2-tetrahydrofuran; or X-COOH wherein X is an alkyl, aryl or arylalkyl of C? -30, straight chain or branched chain (CH2CH2-0) nY COOH or (CH2CH2CH2-0) nY COOH, where Y is a C1 alkyl -10, linear or branched chain is 1-10,000; and I I I wherein Ri and R2 are each independently hydrogen, C? -2 alquilooalkyl, aryl, alkaryl, cycloalkyl or halogen; R3, R4 and R5 (see below) are each independently hydrogen, Ci-20 alkyl or aryl; and R6 is the same or different and is alkyl, aralkyl or an aralkyl radical substituted with alkyl containing about 1 to 20 carbon atoms, as well as oxyalkylated derivatives thereof; and the subscripts x, y, z and p are each integers such that the sum of x, y, z and p can range from about 3 to 20; and x, p and y are each equal to or greater than 1, and z can be 0; and B is -0A0C0CR5CH2, where A is a linear or branched divalent alkylene, from about 1 to 20 carbon atoms, or an oxyalkylated derivative thereof, as described for Re. The method of claim 17, wherein the nonionic surfactant is a polyethylene glycol glyceryl fatty ester of the formula RC (O) 0CH2CH (OH) CH2 (0CH2CH2) nOH where n is 2-200 and RC (O) - is a hydrocarbyl carbonyl group, wherein R is an aliphatic radical having 8-20 carbon atoms. SUMMARY OF THE INVENTION A method for decorating a vitreous substrate with a radiation curable ink composition is described, which consists in applying an ink composition composed of an N-vinyl lactam to the glass in a predetermined design, the ink being operable when cured to bond to the glass. glass substrate, curing the ink on the vitreous substrate exposing it to the radiation by which it is curable, thereby bonding the ink composition to the substrate; and a method for decorating a vitreous substrate with a hot embossing sheet, which consists in applying an ink composition composed of an N-vinyl lactam to the glass in a predetermined design, the ink being operable when cured to bond to the vitreous substrate curing the ink on the glass substrate by exposing it to the radiation by which it is curable, thereby bonding the ink composition to the substrate, pressing a hot stamp sheet against the substrate with a matrix heated to a temperature sufficient to cause a part of the hot foil sheet adheres to the design of the cured, heated ink, but not to the non-ink areas of the glass substrate, removing the matrix, thereby leaving behind a portion of the h. ^ .. nerida to the design of the ink but not to the areas without ink, the glass.