MXPA99010752A - Method and compositions for decorating glass - Google Patents

Abstract

A method for decorating a vitreous article, in particular, a glass substrate, comprising applying to the glass in a predetermined design a radiation curable ink composition which is (i) operable when cured to bond to glass, and (ii) strippable from the glass upon exposure to alkali, and curing the ink on the glass by exposing it to the radiation by which is is curable, thereby bonding the ink to the glass;and related compositions;as well as a method for stripping the decorative indicia from glass upon exposure to alkali, and the related compositions.

Description

"METHOD AND COMPOSITIONS TO DECORATE GLASS" This application is a continuation in part of the co-pending North American Patent Application Case of Attorney's Touch Number Rev 97-2, filed May 23, 1997, entitled "Method and Compositions for Decorating Glass", by the inventors Melvin Edwin Kamen and Ming Hu, for which a Serial Number for the North American Patent Application is not yet available.

TECHNICAL FIELD The invention is in the field of decorating vitreous articles with radiation curable inks. In particular, the invention relates to the decoration of vitreous articles such as glass with radiation curable inks which, to facilitate recycling, are capable of being chemically removed from the glass during the exposure to alkali for a specified period of time.

BACKGROUND OF THE INVENTION Commercial glass and ceramic ware is often decorated by applying a colored ink pattern on the surface of the substrate with stencil printing, offset printing or any other direct application technique. The glass is then baked at high temperatures to bind the design or hint on the surface of the glass. This process, which is sometimes referred to as applied ceramic labeling (ACL), exhibits certain inconveniences. Frequently, the ink compositions contain heavy metals and volatile organic solvents (VOC). Both VOCs and heavy metals are undesirable from the environmental point of view. Second, FTA requires high temperature furnaces for the baking step, which results in considerable energy use and increased potential for worker damage due to the high temperatures at which the process operates. In addition, furnaces at high temperatures are expensive, annoying pieces of equipment that require considerable floor space in factories. The decoration of glass with organic pigmented inks curable by ultraviolet radiation (UV) for the decoration of glassware and ceramics is already known in the art. Organic inks can usually be cured by exposure to radiation, such as ultraviolet radiation, thus avoiding the need for high temperature baking. In addition, ultraviolet light curable organic inks can be formulated to contain little or no VOC or other non-aqueous solvents. Organic inks usually exhibit excellent adhesion to glass. In many countries, it is imperative that beverages such as beer and syrup and siphon soda are sold in returnable glass bottles. After the drink has been consumed, the glass bottles are returned to the beverage filling agent. They are often cleaned, sterilized, refilled and re-labeled and then sold again. Paper labels and decals are most often used to decorate returnable beverage bottles. Both types of labels have many inconveniences. For example, both paper labels and decals are expensive. In addition, they are able to get dirty and can easily peel off when exposed to water or other materials. In addition, many of the adhesives used in decals become sticky when subjected to a bottle cleaning process and cause machines, sewers, etc. They get fat. There is a need for a method for decorating returnable beverage bottles that provides an excellent decorative effect. In addition, the method must be competitive in cost when compared to paper labels and decals. At the same time, the signs - Applied decorative materials should be easily removable from the glass container between filling operations.

COMPENDIUM OF THE INVENTION The invention is directed to a method for decorating a vitreous article comprising the steps: a) supplying the vitreous article in a predetermined design, a radiation curable ink composition that is (i) capable of functioning when cured to bind to the article vitreous, and (ii) removable from the vitreous article when exposed to alkali, b) curing the ink in the vitreous article exposing it to radiation whereby it is curable, thereby ligating the ink in the vitreous article. The invention is also directed to a method for detaching the decorative indicia from a vitreous article decorated with a radiation-cured ink composition containing groups of free acid which is (i) capable of functioning when cured, to bind to the vitreous article, and (ii) releasable from the vitreous article upon exposure to alkali, which comprises contacting the vitreous article with an aqueous alkaline solution containing from 2 to 20 weight percent alkali for a period of about 1 to 120 minutes.

The invention is directed to a glass composition comprising, by weight, the total composition: from 5 percent to 95 percent of an acidic monomer or functional oligomer, from 5 percent to 95 percent of a monomer or oligomer that It does not contain free acid groups, from 5 percent to 95 percent pigment.

DETAILED DESCRIPTION All percentages mentioned herein are percentages by weight, unless otherwise indicated. The radiation curable ink compositions used in the method of the invention should be able to function when cured to bind to the vitreous article, which is preferably glass. In particular, the ink compositions must be capable of adhering to the glass to a sufficient degree to allow use as a commercial container used for beverages or other consumable materials. At the same time, the polymerized ink compositions must be capable of being easily peeled off or removed from the glass during the exposure of the decorated glass to alkali. The glass containers are filled; they are then decorated with radiation curable ink compositions. After the beverage in the container is consumed, the container is returned to the person carrying out the filling. The decorative sign emerges from the glass during the exposure to alkali. The containers are then cleaned, sterilized, refilled, redecorated and shipped again. Generally, the peelable ink compositions are made of radiation curable monomers and / or oligomers having at least one free acid group. The term "free acid" means an acidic group that is capable of reacting with the alkali. Examples of these acidic groups are the carboxylic acid groups, the phosphoric acid groups, the sulfonic acid groups and the like. Preferably, the acid group is a carboxylic acid group. The resulting polymerized coating contains free acidic groups which, upon exposure to the alkali, react with the alkali to form a salt. As a result, decorative signs are more easily removable from glass. It should be noted that in order for the radiation-cured glass coatings to be considered as being "high working", the decorative signs must be able to withstand exposure to a concentrated aqueous alkali solution for a period of two to four hours. In contrast, the radiation cured ink compositions of the invention should be completely removed from the glass container upon exposure to the aqueous alkali within two hours; after a period of about 120 minutes, preferably from 1 to 60 minutes, and more preferably from about 5 to 30 minutes.

INK COMPOSITIONS The Acid Functional Monomer and / or Oligomer The ink compositions used in the method of the invention contain from about 5 percent to 95 percent, preferably from about 10 percent to 85 percent, and of greater preferably from about 15 percent to 75 percent of a monomer, oligomer or low molecular weight homo- or copolymer having at least one free acid group. A variety of these materials are suitable as long as they have at least one free acid group, such as a carboxylic acid, sulfonic acid or phosphoric acid group. The phrase "having at least one free acid group" means that the monomer unit has at least one free acid group, or that the oligomer contains at least one monomer unit containing a free acid group, or if a homo- or copolymer at least one monomer 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 those having carboxylic acid functional groups such as: wherein Ri is H, a straight chain branched from 1 to 30 carbon atoms, substituted or unsubstituted, alkyl, aryl, saturated or unsaturated aralkyl, a pyrrolidone, an aromatic, alicyclic or bicyclic ring substituted or unsubstituted, wherein the substituents are straight chain / branched alkyl of 1 to 30 carbon atoms or halogen.

II. CH2 = C C IOORj wherein Ri is as defined above and R2 is XC OH, wherein X is a straight or branched chain of 1 to 30 carbon atoms of alkyl, aryl, arylalkyl or - (- CH2CH2-0-nY-COO or - (- CH2CH2CH2-O •) • -Y-COOH, wherein Y is a straight or branched alkyl chain of 1 to 10 carbon atoms and n is 1 to 10,000, preferably the monomer or the oligomer of the formula II, wherein Ri is H or CH 3, and R 2 is X-COOH, wherein X is a straight or branched alkyl chain of 1 to 10 carbon atoms, more preferably ethyl Preferably, R 2 is beta-carboxyethyl, eg as in beta-carboxyethyl acrylate, which is sold under the brand name B-CEA by UCB Radcure, Inc. B-CEA is a reactive monomer that contains both acrylate and carboxylic acid functionality, predominantly as the acid dimer acrylic, and in particular, is a mixture of about 40 weight percent beta-carboxyethyl acrylate, approximately 40 per cent or by weight of higher homologs of acrylic acid, and about 20 weight percent of acrylic acid. The B-carboxyethyl acrylate component of this mixture has the following formula: In addition, functional carboxylic acid oligomers, such as aromatic acid methacrylate half-esters and aromatic acid acrylate half-esters are also functional acid oligomers suitable for use in the method of the invention. Examples of these oligomers are the partial esters of anhydride-containing copolymers, such as those disclosed in U.S. Patent No. 4,722,947, which are incorporated herein by reference, these copolymers correspond to the following formula: wherein Ri and R2 each is independently hydrogen, alkyl, aryl, alkaryl, cycloalkyl or halogen of 1 to 20 carbon atoms; R3, R4 and R5 (see below) each are independently hydrogen, alkyl or aryl of 1 to 20 carbon atoms, and Re is the same or different, and is an alkyl, aralkyl or aralkyl radical substituted with alkyl containing about 1 to 20 carbon atoms, as well as the oxyalkylated derivatives thereof; and the subscripts x, y, z, and p, each are integers such that the sum of x, y, z, and p, can vary from about 3 to 20; x, p, e y, each is equal to or greater than 1, and z can be zero; and B is -TAOCOCRsCH2, wherein A_ is a linear or branched divalent alkylene of about 1 to 20 carbon atoms, or - an oxyalkylated derivative thereof, as described for Re. Particularly preferred aromatic partial esters of anhydride-containing copolymers are those sold by Sartomer, Inc. under the Sarbox factory name, such as SB-400, SB-500 and SB- 600 Particular preference is given to the aromatic acid methacrylate half ester between ethoxylated trimethylolpropane acrylate, which is sold by Sartomer, Inc. under the factory name Sarbox 5B500E50. Other suitable functional carboxylic acid monomers include acrylic acid, bisacryloynoacetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, 3-butene-1,2,3-tricarboxylic acid, 2-carboxyethyl acrylate, itaconic acid, methacrylic acid, 4-vinylbenzoic acid and mixtures of these materials. Examples of monomers containing sulfonic acid groups include 2-acrylamido-2-methyl-1-propane sulfonic acid; 2-methyl-2-propene-1-sulphonic acid, 2-propene-1-sulphonic acid, 2-propene-1-sulfonic acid, 4-styrene-sulfonic acid, 2-sulfoethyl methacrylate, internal ammonium salt of 3 -sulfopropyldimethyl-3-methacrylamidopropyl, 3-sulfopropyl methacrylate, vinylsulfonic acid, and so on.

Examples of monomers containing functional groups of phosphoric acid include bis (2-methacryloxyethyl) phosphate, monoacryloxyethyl phosphate and so on.

Additional Polymerizable Reagents In addition, the ink compositions may contain from about 5 percent to 95 percent, preferably, from about 10 percent to 85 percent, most preferably from about 15 percent to 75 percent of other polymerizable reagents , such as radiation curable monomers, oligomers or low molecular weight homo- or copolymers, graft or block terpolymers or copolymers, which do not contain free acid groups. 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 butyrates, methylvinyl ether and methyl methacrylate. , isobornyl acrylate, acrylonitrile or mixtures thereof. Suitable polymers include oligomers, homo- or copolymers, terpolymers, graft copolymers of the aforementioned monomers as long as they have a molecular weight of less than about 50,000, otherwise it is too difficult to effect polymerization, i.e., curing. Preferred are acrylate homopolymers or acrylate or methacrylate copolymers, preferably acrylate or methacrylate copolymers. Examples of these acrylate or methacrylate copolymers include epoxy acrylates, propylene glycol copolymers and a dicarboxylic acid, urethane acrylates and the like. Preferably, the compositions contain one or more polymerizable reagents that are selected from the group consisting of copolymers of urethane acrylic, tripropylene glycol acrylate, epoxy acrylate, and mixtures thereof. Preferably, the radiation curable compositions of the invention contain from about 5 percent to 95 percent by weight of acrylate or methacrylate monomers, or homo- or copolymers that do not contain acid functional groups.

Pigment The compositions used in the invention preferably contain from 5 percent to 95 percent, preferably from 5 percent to 50 percent, most preferably from 8 percent to 35 percent by weight of the total pigment composition. A wide variety of pigments are suitable, including organic and inorganic pigments. Examples of these pigments are noted in U.S. Patent No. 5,178,952, which is incorporated herein by reference. Inorganic pigments include extender pigments such as bariites, barium sulfate, calcium carbonate, talc, clay, alumina, titanium dioxide, white carbon, Chinese white, zinc sulfide, lithopone, ultramarine, Prussian blue, cobalt, chromium oxide , green-yellow of viridian chrome, 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, vat pigments, lacquers, phthalocyanine pigments and so on. The preferred pigment for imparting white color to the ink composition is titanium dioxide. Preferred red and yellow pigments are isoindolinones and pyrrolopyrroles, as disclosed 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 in U.S. Patent No. 5,571,359, issued to Kamen et al., all of which are incorporated herein by reference. These pyrrolopyrroles, usually from wherein Ri and R2 are preferably alkyl, arylalkyl, aryl, substituted or unsubstituted isocitic or heterocyclic aromatic radicals; R3 and R4 are each independently H, substituted or unsubstituted alkyl, alkoxycarbonyl, aroyl (eg benzoyl), arylalkyl (eg benzoyl), aryl (eg phenyl), alkanoyl, cycloalkyl of 5 to 6 carbon atoms, alkenyl, alkynyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl or alkoxycarbonyl; and X is O or S. Preferred is a compound wherein Ri and R2, each independently is phenyl or naphthyl, R3 and R4 are hydrogen and X is O. Particularly preferred as the red pigment is pyrrolo, 3,4-C-pyrrol-l, 4-dione , 2,5-dihydro-3,6-di-4-chlorophenyl, which has a CAS number 84632-65-5 and which is known by the common name of CI red pigment 254. This pigment can be obtained commercially from Ciba-Geigy Pigments Division, of Newport, DE, under the name of factory Irgazin DPP Red 80. Other red pigments of Ciba-Geigy sold under the name of factory Irgazin are also suitable. Suitable isoindolinones are 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 the alkyl esters of tetrachlorocyanobenzoic acid, particularly benzoic acid, the 2,3,4,5-tetrachloro-6-cyano-methyl ester, which is reacted with 2-methyl-1,3-benzenediamine and sodium methoxide. This pigment composition has a common name of C.I. Pigment Yellow 109 and can be obtained commercially from Ciba-Geigy Pigments Division, of Newport, DE, under the name of Irgazin Yellow 2 GLTE factory. Other pigments in the Irgazin Yellow series, as manufactured by Ciba-Geigy are also appropriate. Particularly suitable are the blue pigments sold by Ciba-Geigy under the factory name Irgazin Blue X-3367, or by Whittaker, Clark & Daniels under the factory name Ultramarine Blue 5009.

Defoaming Agent The ink compositions used in the invention also preferably contain from about 0.01 percent to 10 percent of a defoaming agent, preferably a polyether-containing defoaming agent, which will cause the ink to be uniformly applied. on the glass substrate without bubbles or inequalities. A wide variety of defoaming agents are suitable, but the defoaming agents sold by BYK Chemie under the factory name BYK are preferred. Examples of these defoaming agents are the alkylvinyl ether polymers which are set forth in US Pat. No. 5,187,201, which is incorporated herein by reference. Examples of other defoaming agents include polyethers such as BYK-052, BYK-053 and BYK-033. The BYK-052 and -053 are polyethers such as polyethylene or polypropylene glycol ethers, and in particular, polyvinyl ethers. Also suitable is BYK-354 which is a polyacrylate solution and BYK-022 which is a mixture of hydrophobic solids and polysiloxane polyglycol foam destruction. Preferably, the polyether defoaming agent is an ethoxylated alkyl phenol, more particularly a mixture of petroleum distillates and an ethoxylated alkylphenol, such as that sold by BYK-Chemie under the tradename BYK-033.

Adhesion Promoter The ink compositions used in the invention also preferably contain from about 0.01 percent to 25 percent, preferably from about 0.05 percent to 15 percent, and most preferably from about 0.1 percent to 5 percent of a silane adhesion promoter that will improve the adhesion of the cured resin to the glass surface. Examples of silane are silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, amino silanes or isocyanate silanes. Suitable silanes include organofunctional silanes of the formula: where n = 0 - 3 a = 0 - 2 Y = NH "CH, = CH, CH, = C-COO-, CHrNH-, NH, -CO-NH-, HS-, Cl-, NH, (CH ,), NH-, 1 CH3 H - cH -; O = C = N-; X is each independently is CH3, Cl, COCH3, OC2H4OCH3, (OC2H4) 2? CH3 or -OR, wherein R is a straight or branched chain alkyl of 1 to 20 carbon atoms, preferably methyl or ethyl. Silanes having this formula can be obtained commercially under the Dynasylan brand of Huís, America, Inc., of Piscataway, New Jersey or Osi.

Specialties Inc. Other organofunctional silanes, such as those disclosed in U.S. Patent No. 5,221,560, which is incorporated herein by reference are also appropriate. These organosilanes are acriloxifuncionales silanes including 3-methacryloxypropyltrimethoxysilane, 3 -acriloxipropiltrimetoxisilano, 2 -metacriloxieti1trimetoxisilano, 2-acryloyloxyethyltrimethoxysilane, 3 -metacriloxipropiltrietoxisilano, 3-acriloxipropiltrimetiloxisilano, 3 -acriloxipropiltrietoxisilano, 2 -metacriloxietiltrietoxisilano, 2 -metacriloxietiltrietoxisilano, 2-acriloxietiltrietoxisilano, etc. Suitable glycidaxy silanes include 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethylsilane, and so on. Acryloxy-functional silanes, isocyanate silanes and amino silanes are preferred for use in the compositions of the invention. The preferred acryloxy functional silane is 3-methacryloxypropyltrimethoxysilane, which is sold by Huís America Inc., under the factory name DYNASYLAN MEMO. The preferred aminosilane is sold by Huís America Inc., under the factory name DYNASYLAN TRIAMO. The preferred Isocyanate silane is sold by Osi Specialties Inc., under the factory name A-1310. In the preferred ink compositions of the invention, a mixture of three silanes is generally preferred from 0.01 percent to 2 percent by weight each.

Surfactant The ink compositions also preferably contain from 0.01 percent to 20 percent, preferably from 0.5 percent to 10 percent and more preferably from 1 percent to 5 percent by weight of a fluorinated surfactant. The term "fluorinated surfactant" means a fluorine-containing compound having at least one lipophilic group or a portion of at least one hydrophilic group or portion.

In particular, fluorocarbon or fluorosilicone surfactants are especially desirable. Suitable surfactants include those set forth in U.S. Patent No. 4,961,976 which is incorporated herein by reference. Fluorocarbon surfactants such as those sold under the trademark Fluorad by 3M Company are preferred. These fluorochemical surfactants include fluorinated alkyl esters, polyoxyethylene fluorinated alkyl ethanol and the like. Particularly preferred are non-ionic fluorinated alkyl alkoxylates, e.g. those sold by 3M under the brand FC-171. Preferred are fluorinated alkyl ethoxylates and propoxylates of 1 to 30 carbon atoms.

Photoinitiator The ink compositions preferably contain a photoinitiator which catalyzes the polymerization of the monomers upon exposure to radiation whereby the monomers are curable. In general, there are two types of photoinitiators: free radical and cationic. Free radical initiators are most commonly used with ethylenically unsaturated monomers and oligomers, while cationic photoinitiators are used with functional vinyl ether or epoxy resins. The 2 - Suitable free radical type photoinitiators include carbonyl compounds such as ketones, acetophenones, benzophenones and derivatives thereof. Examples of these materials include, for example, methylethyl ketone; benzophenone; benzyldimethyl ketal; 1-hydroxycyclohexylphenyl ketone; diethoxyacetophenone; 2-methyl-1- (methylethiophenyl) -2- (4-morpholinyl) -1-propanone; 2-benzyl-2-N, N-dimethylamino-l, 4 (4-morpholinophenyl) -1-butanone; 2,2-dimethoxy-2-phenylacetophenone; 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropan-l-one; 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 4- (2-hydroxyethoxy) phenyl-2 (2-hydroxy-2-methylpropyl) Latone; and a phosphine oxide mixture of bis (2,6-dimethyloxybenzoyl) -2-4-4-trimethyl Pentyl and 2-hydroxy-2-methyl-1-phenyl-propan-1 -one. A mixture of 25 percent phosphine oxide of bis (2,6-dimethioxybenzoyl) -2-4-4-trimethylpentyl and 75 percent of 2-hydroxy-2-methyl-1-phenyl-propan-1 is preferred. ona, which is sold under the factory name Irgacure 1700 by Ciba-Geigy. Small amounts of cationically curable monomers or oligomers can be used in the compositions of the invention, for example, less than about 10 percent, preferably less than about 5 percent by weight of the ink composition. However, the cationically cured compositions generally exhibit a high resistance to bonding to glass such that if they are used in considerable amounts in the compositions of the invention the ink will not be released from the glass upon exposure to the alkali. If cationically curable monomers or oligomers are used in the compositions of the invention, it is desirable to use cythionic photoinators. The term "cationic photoinitiator" means a molecule or ingredient that during the 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 actinic or ultraviolet light radiation instead of the electron beam, it is desirable to add a cationic photoinitiator that catalyzes the crosslinking of the resin upon exposure to the radiation to which the resin is sensitive. On the other hand, if the ink compositions of the invention are cured with an electronic beam, it may be possible to avoid the cationic photoinitiator. Various types of cationic photoinitiators are suitable. Both ionic cationic photoinitiators, such as onium salts or organometallic salts are suitable as well as non-ionic cationic photoinitiators, such as organosilanes, latent sulfonic acids and the like. Preferred are the photosensitive onium salts, in particular, onium salts such as those disclosed in US Patent Nos. 4,058,401, 4,138,255, 4,161,478, 1,175,972 all of which are incorporated herein by reference. Particularly preferred are the triarylsulfonium salts, in particular the triarylsulfonium salts, such as those sold by Union Carbide under the trade name Cyracure UVI 6990 and 6974. Ferrocenium salts, such as those sold under the name Irgacure, are also suitable. by Ciba-Geigy, in particular, Irgacure 261. Sulfonyloxy ketones and silylbenzyl ethers are also good cationic photoinitiators. A detailed analysis of the mechanism of cationic cure is disclosed 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, called "Photoinitiators for Free Radical and Cationic Polymerization, K.K. Dietliker, pages 332-374 (1991), both of which are incorporated herein by reference. The photosensitive onium salts are used as photoinitiators in cationic cure, in particular the onium salts such as those disclosed in US Patent Nos. 4,058,401, 4,138,255, 4,161,478, 4,175,972, all of which are incorporated herein by reference. Especially preferred are the triarylsulfonium salts, in particular the salts of - triarylsulfonium such as those sold by Union Carbide under the trade name Cyracure UVI 6990 and 6974. The photoinitiator is generally present at from about 0.1 percent to 15 percent, preferably from about 0.5 percent to 12 percent, and more preferably from about 0.5 percent to 10 percent by weight of the total composition. The preferred ink compositions used in. The invention comprises: from 5 percent to 95 percent of an ethylenically unsaturated monomer or oligomer containing at least one group of free acid, from 5 percent to 95 percent of a pigment, and from 5 percent to 95 percent percent of a monomer or oligomer free of acid groups. More preferably, the ink compositions further comprise an ingredient that is selected from the group consisting of from about 0.1 percent to 25 percent of a silane adhesion promoter, from about 0.01 percent to 10 percent of a defoaming agent. of polyether, from about 0.01 percent to 20 percent of a fluorinated surfactant, and from about 0.1 percent to 1 percent of a photoinitiator.

THE METHOD OF DECORATION The term "ceramic" or "vitreous article" when used in accordance with the invention will mean glass, ceramics, mosaic and similar vitreous materials. The articles that can be decorated or embossed in accordance with the method of the invention can have any configuration or shape, such as a container, a sheet, a mosaic, a figurine or the like. In the preferred embodiment of the invention, the article is made of glass or ceramic and is a package, such as a cosmetic or beverage container. The ink composition is applied to the article to be decorated in a predetermined pattern using a variety of printing methods, including stencil printing, offset printing, engraving, hand painting and the like. After the ink is applied to the substrate or to the article it is irradiated with ultraviolet light or active radiation using a conventional ultraviolet light source. The term "UV" means ultraviolet light, which generally has a wavelength of 4 to 400, preferably 325 to 400 nanometers. The term "actinic" means radiation having a wavelength of 200 to 600 nanometers. The electronic beam can be used instead of a source of ultraviolet light. If an ultraviolet transporter is used, it is established that the - The substrate passes through the radiation beam for an appropriate period of time to completely cure the ink composition and cause it to adhere to the substrate. If desired, the substrate can be moved through the conveyor in one or more passes to achieve the required cure. The appropriate time varies depending on the ink formula, but it is usually completed by healing in a period of time ranging from fractions of one second to 30 minutes. It is preferred that by the time the decorated substrate or article is removed from the conveyor, the ink has completely cured and melted on the surface of the substrate. In some cases it may be necessary to subject the newly stamped glass container to a slightly elevated temperature, rather than UV curing of the ink applied to the substrate, or to an additional post-ultraviolet heat curing application to finally polymerize the ink in the substrate. Preferably, the decorated substrate is subjected to post-ultraviolet cure heating at a temperature of 90 ° C to 2000 ° C, preferably 100 ° C to 200 ° C for a period of 0.5 to 30 minutes. The ink compositions are well suited for use in automatic systems such as the multi-color printing apparatus disclosed in copending application Serial No. 432,485, filed - on May 1, 1995 by Kamen et al., entitled "Apparatus and Method Eor Screen Printing Radiation Curable Compositions" or with the methods disclosed in U.S. Patent Number 5,562,951, both of which are incorporated herein by reference. In another embodiment of the invention, it is possible to prepare an ink composition of the invention without the pigment and to stamp it on the glass substrate in a predetermined design according to the methods described above. For example, a substrate such as a container can be decorated in a predetermined pattern by silk stenciling the non-pigmented ink composition on the substrate and curing with the appropriate radiation. A layer of a hot stamp sheet is then pressed against the substrate with. a press that is heated to a temperature sufficient to cause the hot stamping sheet to adhere to the stamped ink design but not in the ink-free areas of the glass. The hot foil sheet is usually a laminate comprising a carrier material (often polyester or a similar material capable of being released), a release film between the carrier and a subsequent decorative layer that is usually in color or a metallized layer , more often aluminum or colored aluminum. The sheet may contain other optional layers such as one or more protective layers, layers of hot melt adhesive, etc. between the metallized layer or the layers and the carrier material. More specifically, the hot stamping sheet can be defined as a multilayer continuous tape comprising a backing film carrier, a release liner, one or more protective top coatings, one or more color coatings, and a hot melt adhesive in that order .. The hot foil sheet is then pressed against the package with the hot melt adhesive layer being compressed against the substrate. The compression, which may be a normal hot stamping press or a hand press, is heated to a temperature sufficient to cause the hot melt adhesive layer of the hot stamp sheet to adhere to the ink decorated portion of the substrate. . Generally, this temperature varies from approximately 121 ° C to 2040 ° C. Higher temperatures than this can cause deterioration of the hot stamping sheet. The application of heat causes the adhesive side of the stamping foil to adhere adhesively to the ink pattern but not to the ink-free areas of the substrate. When the compression is removed, a portion of the sheet laminate adheres to the ink decoration but not to the ink-free areas of the glass. In particular, adhering to the ink design on the substrate there is a hot melt adhesive layer, the color coatings and the protective top coatings, in that order, of the hot stamp sheet. The release coating portions may or may not adhere to the protective topcoat because the release coating is designed to melt during the application of heat and cause the backing layer of the polyester carrier to be released from the coating layer. Superior protector and some residue may remain. The resulting hot stamped substrate exhibits a metallic appearance of gold, silver, or colored, depending on the color of the hot stamping foil. In yet another embodiment of the invention, it is possible to provide a decorated substrate having a two tone effect wherein all or a portion of the colored ink in the substrate is hot stamped. In this case, a pigmented ink composition is applied to the substrate in a predetermined design and cured by exposing it to the radiation whereby it is curable for a sufficient time to effect the. complete healing The hot stamping sheet is applied as described above either to the entire ink design or only to one part (ie, complete record - or partial). If the hot stamp sheet is applied in the partial register, or is applied to a portion of a pigmented ink design, a pleasant two tone effect is achieved. Many times it is more economical to stamp the entire design on the substrate using colored ink and then hot stamping on the desired portion of the design, instead of applying clear and hot stamping ink and then stamping the colored tape on the desired design on a second application. The ink compositions of the invention provide sufficient adhesion to the glass as well as exhibit sufficient resistance to scraping and scoring to make the decorated articles suitable for use in bottles for beverages and commercial cosmetics. _ THE DETACHMENT METHOD The ink compositions of the invention can be removed from the glass when exposed to glass to alkali. In particular, the free acid groups found in the polymerized glass composition are capable of reacting with the hydroxyl groups of the base to form a salt that is easily detached or removed from the glass. The aqueous alkaline solution comprises from about 1 percent to 20 percent, preferably from about 2 percent to 15 percent, most preferably from about 2 percent to 12 percent, by weight of alkali. Suitable alkali materials include metal hydroxides (e.g., alkali metal and alkaline earth metal hydroxides) such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like. The cured ink compositions should be removed from the glass upon exposure to the aqueous alkali after a period of about 1 to 120 minutes, preferably about 1 to 60 minutes and more preferably about 1 to 30 minutes. The glass substrate is usually immersed in the aqueous alkaline solution for an appropriate period of time after which the. Ink compositions are removed from the glass surface. Preferably the glass container is subjected to an aqueous alkaline solution at a temperature of 60 ° C to 1000 ° C, more preferably 70 ° C to 950 ° C. and especially preferably from 72 ° C to 900 ° C. In the especially preferred embodiment of the invention, the ink composition is removed from the glass containers after exposure of the glass to a 4 percent aqueous solution (approximately) of - Sodium hydroxide at a temperature of 70 ° C to 1000 ° C, after 1 to 15 minutes. The decorating method and the compositions of the invention are excellent for use in glass containers used in the returnable beverage market. The decorative indicia applied in accordance with the invention remain on the glass during the shelf life of the package, but can nevertheless be easily removed upon exposure to an aqueous alkaline solution. This eliminates the need for paper labels and decals, which results in significant cost savings. Also, the signs are much more aesthetically pleasing, similar to the aesthetic achieved by ACL. Therefore, beverage and cosmetics manufacturers are able to offer glass containers that provide aesthetics similar to ACL, with indications that can be easily removed when exposed to alkali solutions when the glass container is returned to the person performing the treatment. fill . The invention will be further described in relation to the following examples, which are indicated for purposes of illustration only.

EXAMPLE 1 - A white ink composition was made in the following manner: grams% by weight Dipentaerythritol Pentaacrylate ^ - 25.0_ 24.8 Epoxy acrylate + tripropylene glycol acrylate- ^ 27.0 26.8 semi-ester of aromatic acid methacrylate in ethoxylated trimethylolpropane triacrylate ^ 5.0 5.0 Beta-carboxyethyl acrylate ^ 10.0 9.9 Aromatic urethane acrylate with polyacrylated polyol diluent ^ 10.0 9.9 Titanium dioxide (pigment) 17.0 16.9 Irgacure 1700 ^ 3.0 3.0 Gamma-isocyanotropyltriethoxysilane7 0.5 0.5 3-methacryloxypropyltrimethoxysilane ^ Q.5 0.5 Trimethoxysilylpropyl-ethylenetriamine9 0.5 0.5 Fluoroalkylated alkoxylate10 0.5 _ 0.5 BYK-03311 1.0 1.0 Modaflow12 0.8 0.8 SR399, Sartomer Company, Inc. (another polymerizable reagent) CN104, Sartomer Company, Inc. (another polymerizable reagent) SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) B-CEA, UCB Radcure Inc. ( polymerizable reagent with free acid group) EB-220, UCB Radcure Inc. (another polymerizable reagent) Ciba-Geigy Corp. Mixture of 25 weight percent bis (2,6-dimethylobenzoyl) -2,4-, 4-trimethylpentylphosphine oxide and 75 weight percent of 2-hydroxy-2-methyl-1-phenylpropan -1-ona. (photoinitiator) A-1310, Osi Specialties, Inc. (adhesion promoter) DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) DYNASYLAN TRIAMO, Huís America Inc. (adhesion promoter) FC-171, 3M Company (surfactant) BYK-033, BYK-Chemie. A mixture of 92 weight percent petroleum distillates and 5 weight percent ethoxylated alkylphenol (defoaming agent). Modaflow, Monsanto, Inc. Ethyl acrylate and 2-ethylhexyl acrylate copolymer (defoaming agent) EXAMPLE 2 A blue ink composition was made in the following manner; grams% by weight Dipentaerythritol Pentaacrylate ^ 25.0 23.9 Epoxy acrylate + tripropylene glycol acrylate- ^ 27.0 25.8 semi-ester of aromatic acid methacrylate in trimethylolpropane triacrylate petoxyl- ^ 5.0 4.8 Beta-carboxyethyl acrylate ^ 10.0 9.6 Aromatic urethane acrylate with polyol diluent polyacrylate ^ 10.0 9.6 Ultramarine blue 500913 20.0 19.1 Irgazin blue X-336714 1.0 0.9 Irgacure 1700 ^ 3.0 2.9 Gamma-isocyanotropyltriethoxysilane7 0.5 0.5 3-methacryloxypropyltrimethoxysilane8 0.5 0.5 Trimethoxysilylpropyl-ethylheneyl triamine 0.5 0.5 Fluoroalkylated alkoxylate 0.5 0.5 BYK-03311 1.0 1.0 Modaflow ^ -2 0.5 0.4 SR399, Sartomer Company, Inc. (another polymerizable reagent) - CN104, Sartomer Company, Inc. (another polymerizable reagent) SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) B-CEA, UCB Radcure Inc. (polymerizable reagent with free acid group) EB-220, UCB Radcure Inc. (another polymerizable reagent) Ciba-Geigy Corp. Mixture of 25 weight percent bis (2,6-dimethylobenzoyl) -2,4-, 4-trimethylpentylphosphine oxide and 75 weight percent of 2-hydroxy-2-methyl-1-phenylpropan -canvas. (photoinitiating agent) - A-1310, Osi Specialties, Inc. (adhesion promoter) DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) • DYNASYLAN TRIAMO, Huís America Inc. (adhesion promoter) FC-171, 3M Company (surfactant) BYK-033, BYK-Chemie. A mixture of 92 weight percent petroleum distillates and 5 weight percent ethoxylated alkylphenol (defoaming agent). Modaflow, Monsanto, Inc. Ethyl acrylate and 2-ethylhexyl acrylate copolymer (defoaming agent) Wittaker, Clark, & Daniels (pigment) - 4 Ciba Pigment Division EXAMPLE 3 A white ink composition was made in the following manner: grams% by weight semi-ester of aromatic acid methacrylate in trimethylolpropane triacrylate ethoxylate 25.0 24.5 Beta-carboxyethyl acrylate 35.0 34.2 Monofunctional acrylate resin ^ 15.0 14.7 Epoxy acrylate + tripropylene glycol acrylate ^ 5.0 4.9 Titanium dioxide 15.0 14.7 Irgacure 1700 ^ 3.0 2.9 BYK-0336 1.0 1.0 3-methacryloxypropyltrimethoxysilane7 0.6 0.6 Gamma-isocyanopropyltriethoxysilane _0.6 0.6 Methyl diethanolamine 2..0 1.9 SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) B-CEA, UCB Radcure Inc. (polymerizable reagent with free acid group) 3 _ Aromatic oligomer containing suspended carboxy functional groups, Henkel Corporation (reagent polymerizable with free acid group) CN104, Sartomer Company, Inc. (another polymerizable reagent) Ciba-Geigy Corp. 25% by weight mixture of bis (2,6-dimethoxybenzoyl) -2, 4-, 4- oxide tri ethylpentylphosphine and 75 weight percent of 2-hydroxy-2-methyl-1-phenylpropan-1-one. (photoinitiator) BYK-Chemie, A mixture of 92 percent by weight of petroleum distillates and 5 percent by weight of ethoxylated alkylphenol (defoaming agent) DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) A-1310, Osi Specialties, Inc. (adhesion promoter) The ingredients were combined and mixed well.

EXAMPLE 4 An ultramarine blue composition was made in the following manner: grams% by weight semi-ester of aromatic acid methacrylate in ethoxylated trimethylolpropane triacrylate ^ 25.0 24.2 Beta-carboxyethyl2 acrylate 30.0 29.1 Monofunctional acrylate resin3 15.0 14.5 Epoxy acrylate + tripropylene glycol acrylate ^ 5.0 4.8 Irgazin Blue X-3367 ^ 1.0 1.0 Ultramarine Blue 50096 20.0 19.4 Irgacure 17007 3.0 2.9 BYK-0338 1.0 1.0 3-methacryloxypropyltrimethoxysilane ^ 0.6 0.6 Gamma-isocyanotropropyltriethoxysilane10 0.6 0.6 Methyl dietanolamine 2.0 1.9 SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) B-CEA, UCB Radcure Inc. (polymerizable reagent with free acid group) Aromatic oligomer containing suspended carboxy functional groups, Henkel Corporation (reagent polymerizable with free acid group) CN104, Sartomer Company, Inc. (another polymerizable reagent) 5 Ciba Pigment Division (pigment) 6 Whittaker, Clark, & Daniels (pigment) 7 Ciba-Geigy Corp. 25 percent by weight mixture of bis (2,6-dimethoxybenzoyl) -2,4-, 4-trimethylpentylphosphine oxide and 75 percent by weight of 2-hydroxy-2- methyl-l-phenylpropan-l-one. (photoinitiating agent) 6 BYK-Chemie, A mixture of 92 percent by weight of. petroleum distillates and 5 weight percent ethoxylated alkylphenol (defoaming agent) 7 DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) 8 A-1310, Osi Specialties, Inc. (adhesion promoter) The ingredients were combined and they mixed well, EXAMPLE 5 A white ink composition was made as follows: grams% by weight half ester of aromatic acid methacrylate in ethoxylated trimethylolpropane triacrylate1 25.0 22.8 Epoxy Acrylate + Acrylate - tripropylene glycol2 1Q.0 9.1 Beta-carboxyethyl acrylate- ^ 30.0 27.3 Monofunctional acrylate resin ^ 15.0 13.7 Polytetrafluoroethylene ^ 1.0 0.9 Titanium dioxide - 17.0 15.5 Iragacure 1700 ^ 3.0 2.7 BYK-0337 1.5 1.4 3-methacryloxypropyltrimethoxysilane i 0.6 0.5 Gamma-isocyanothropyl-ethylenediamine triamine 0.6 0.6 Monodiethanolamine 3.0 2.8 Benzophenone 3.0 2.8 SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) CN104, Sartomer Company, Inc. (another polymerizable reagent B-CEA, UCB Radcure Inc. (reagent polymerizable with free acid group) Aromatic oligomer containing groups suspended carboxy functional groups, Henkel Corporation (polymerizable reagent with free acid group) 5 SST-4, Shamrock Technologies, Inc. (thickening agent) 6 Ciba-Geigy Corp. 25% by weight mixture of bis (2, 6-dimethoxybenzoyl) -2,4-, 4-trimethylpentylphosphine and 75 weight percent of 2-hydroxy-2-methyl-1-phenylpropan-1-one. (Photoinitiating agent) 7 BYK-Chemie, A mixture of 92 weight percent petroleum distillates and 5 weight percent alkylphenol (defoaming agent) 7 DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) 8 A-1310, Osi Specialties, Inc. (adhesion promoter) The composition It was elaborated by combining the ingredients and mixing the ingredients well.

EXAMPLE 6 A blue ink composition was made according to the following formula: grams% by weight is ester of aromatic acid methacrylate in trimethylolpropane triacrylate ethoxylate 25.0 24.7 Tripropylene glycol2 epoxy acrylate t acrylate 10. 0 9. 9 Beta-carboxyethyl- ^ 25 acrylate. 0 24. 7 Monofunctional acrylate resin4 15. 0 14. 8 Ultramarine blue 5009 ^ 15. 0 14. 8 - Blue Irgazin X-3367 ^ 1.5 1.5 Polytetrafluoroethylene7 1.0 1.0 Iragacure 1700 ^ 3.0 3.0 Benzophenone 3.0 3.0 BYK-0339 1.5 1.4 3-methacryloxypropyltrimethoxysilane10 0.6 0.5 Gamma-isocyanotropropyltriethoxysilane 0.6 0.5 SB500 E50, Sartomer Company, Inc. (polymerizable reagent with free acid group) CN104, Sartomer Company, Inc. (another polymerizable reagent) B-CEA, UCB Radcure Inc. (polymerizable reagent with free acid group) Aromatic oligomer containing suspended carboxy functional groups, Henkel Corporation (polymerizable reagent with free acid group) 5 Whittaker, Clark, & Daniels (pigment) 6 Ciba Pigment Division (pigment) 7 SST-4, Shamrock Technologies, Inc. (thickening agent) Ciba-Geigy Corp. 25 percent by weight mixture of bis (2,6-dimethoxybenzoyl) -2,4-, 4-trimethylpentylphosphine oxide and 75 percent by weight of 2-hydroxy-2-methyl-1-phenylpropan -1-ona. (photoinitiating agent) - BYK-Chemie, A mixture of 92 percent by weight of petroleum distillates and 5 percent by weight of ethoxylated alkylphenol (defoaming agent) 10 DYNASYLAN MEMO, Huís America Inc. (adhesion promoter) 11 A-1310, Osi Specialties , Inc. (adhesion promoter) The ingredients were combined and mixed well.

EXAMPLE 7 The white ink composition of Example 2 was applied to the alcoholic beverage bottles by stenciling with a 230 mesh screen using an Autoroll M-25 semi-automatic stencil stamping machine. The ink in the bottle was stamped by exposure to ultraviolet light from a P600 power supply having a D focus of 9 millimeters. The cure rate was less than one second per bottle. Then, the blue ink of Example 2 was stamped to the bottle in partial registration with the white ink cured. The ink cured when exposed to the ultraviolet light source. The bottle was then subjected to post-heat cure at a temperature of 100 ° C for 30 minutes. The signs adhered well to the bottle and exhibited a real bright coloration.

EXAMPLE 8 The finished bottles decorated according to Example 7 were immersed in a water bath containing 4 percent sodium hydroxide at a temperature of 72 ° C. The cured inks were completely removed from the bottles after 4 minutes. Even though the invention has been described in relation to the preferred embodiment, it is not intended to limit the scope of the invention to the specific form indicated, but on the contrary it is intended to protect those alternatives, modifications and equivalents that may be included within the scope of the invention. spirit and scope of the invention as defined by the appended claims.

Claims (27)

- CLAIMS:

1. A method for decorating a vitreous article comprising the steps of: a) applying to the vitreous article in a predetermined design a radiation curable ink composition that is (i) capable of functioning when cured to bind to the vitreous article, and (ii) ) detachable from the vitreous article when exposed to alkali. b) curing the ink in the vitreous article exposing it to radiation, whereby it is curable, thus ligating the ink to the vitreous article.

2. The method of claim 1, wherein the alkali is an aqueous alkaline solution.

3. The method of claim 2, wherein the aqueous alkaline solution consists of 2 percent to 10 percent by weight alkali.

4. The method of claim 3, wherein the alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide.

The method of claim 4, wherein the alkaline solution contains 4 weight percent sodium hydroxide.

The method of claim 1, wherein the ink composition is capable of being detached from the vitreous article upon exposure to an aqueous alkaline solution containing from 2 percent to 20 weight percent alkali, at a temperature of 60 ° C at 100 ° C after 1 to 60 minutes.

The method of claim 1, wherein the ink composition comprises a monomer or an oligomer having at least one free acidic group.

The method of claim 7, wherein the acidic group is a carboxylic acid group, a phosphoric acid group or a sulfonic acid group.

9. The method of claim 7, wherein the monomer or oligomer is an ethylenically unsaturated monomer or oligomer.

The method of claim 9 wherein the ethylenically unsaturated monomer or oligomer is an acrylate or methacrylate.

The method of claim 10 wherein the acidic group is a carboxylic acid group.

The method of claim 11, wherein the monomer or oligomer contains repeating alkylene oxide units.

The method of claim 11, wherein the monomer or oligomer is an aromatic acid anhydride. - -

14. The method of claim 1, wherein the ink composition comprises, by weight of the total composition: from about 5 percent to 95 percent of an ethylenically unsaturated monomer or oligomer having at least one free acid group, about 5 percent to 95 percent of a pigment.

15. The method of claim 14 wherein the ink composition further comprises from about

0. 5 percent to 25 percent of a silane adhesion promoter.

16. The method of claim 14 wherein the ink composition further comprises from about 0.01 percent to 10 percent of a polyether defoaming agent.

17. The method of claim 14 wherein the ink composition further comprises a fluorinated surfactant.

18. The method of claim 1, wherein the ink is curable by exposure to actinic radiation.

19. The method of claim 1, wherein the ink is curable by exposure to ultraviolet radiation. -

20. The method of claim 1, wherein the vitreous article is glass.

21. A method for detaching the decorative indicia from a glass substrate decorated with a radiation-cured ink composition containing free acid groups that is (i) capable of functioning when cured to bind to. a glass and (ii) removable from the glass when exposed to alkali, which comprises contacting the glass substrate with an aqueous alkaline solution containing from about 2 percent to 20 weight percent alkali for a period of 1 to 60 minutes .

22. The method of claim 21 wherein the glass substrate is contacted with the aqueous alkaline solution at a temperature of about 60 ° C to 100 ° C.

23. The method of claim 21 wherein the radiation cured ink composition is a polymeric composition formed by the polymerization of ethylenically unsaturated monomers or oligomers having at least one free acid group.

24. The method of claim 23 wherein the ethylenically unsaturated monomers or the oligomers are acrylates or methacrylates. - -

25. The method of claim 23 wherein the acid group is a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.

26. The method of claim 25 wherein the acid group is a carboxylic acid group.

27. The invention is directed to an ink composition comprising the weight of the total composition: from about 5 percent to 95 percent of an ac functional monomer or oligomer, from about 5 percent to 95 percent of a monomer or oligomer that does not contain, free acid groups. from about 5 percent to 95 percent of a pigment.