MXPA01001267A - Screen coating composition and method for applying same - Google Patents

Abstract

A substantially water-free, water-washable, energy-curable composition includes an epoxy oligomer and/or urethane oligomer having at least two ethylenically unsaturated moieties, at least one alkoxylated polyol monomer having at least two ethylenically unsaturated moieties and capable of being copolymerized with the oligomer, and a surface active agent capable of being integrated into the molecular structure of the cured polymer and further capable of rendering the uncured composition dispersible in water. Optionally, the composition can contain a photoinitiator. The composition is self-dispersible in water and is especially suitable for use as a coating material for a printing screen.

Description

COMPOSITION OF STRETCH COATING AND METHOD TO APPLY THE SAME BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a polymer formation composition, energy curable, water washable, water-free, especially useful as a printing stencil coating, and a method for applying the same.

Background of the Technique,. In printing with silk screen, the ink is forced onto a printing substrate through a stencil, or "mask", having a porous stencil area configured in the shape of the markings to be printed, such as letters or graphic images. The printing substrate can be paper, textile, metal, ceramics, polymeric film, and the like. The stencil may be a gauze or mesh made of metal, textile fabric such as silk or cotton, or various polymer materials. The mask is usually prepared by coating a stencil with a curable composition, curing the composition, and then etching the marks. The etched areas are porous, thus allowing the ink to be forced through the stencil to the printing substrate to print the marks. After printing, the ink on the substrate is cured or hardened by any of several methods, such as by example, exposure of the ink to energy such as heat or radiation (v.gr ultraviolet, electronic beam, and the like) evaporation of a solvent in the ink composition, or oxidation hardening of the drying oil components (v.gr linseed oil, tung oil), and the like 1 5 The three main technologies that are currently practiced that make up the volume of coatings and inks include zero volatile organic compounds (VOC) carried by solvent, carried by water. Systems carried by solvent and carried or water produced coatings that are washable Water washing ability is a desired feature of a coating composition since the coating application equipment needs to be cleaned for new use. However, there has been a technological push to remove organic solvents and water in Such compositions Organic solvents present environmental health issues And both Solvent-based systems such as water-based are energy intensive, requiring drying ovens to remove solvent or water. For example, thermally induced drying and curing of coated screen fabric typically requires about 7,000 to 12,000 ilojoules of energy per kilogram of fabric as well as a prolonged curing time, typically several hours. Consequently, what is desired is a VOC composition of zero, without water, however dispersible in water which would be particularly useful as a coating for a printing stencil.

COMPENDIUM OF THE INVENTION In accordance with the present invention, there is provided an energy-curable, water-washable, substantially water-free polymer composition comprising 2 or 3) an oligomer selected from the group consisting of oligomer epoxy and urethane oligomer, the oligomer having at least two polymerizable, ethylenically unsaturated fractions; 5 b) at least one alkoxylated polyol monomer having at least two polymerized, ethylenically unsaturated fractions and capable of being copolymerized with component (a) of oligomer to provide a solid cured polymer when exposed to energy polymerization conditions; and) at least one surfactant capable of being integrated into the molecular structure of the polymer resulting from the copolymerization of (a) and (b) either by covalent bond or by hydrogen bonding, and further capable of making the composition dispersible in water. Also provided herein is a method for coating a stencil with the above-mentioned composition employing water-washed applicator means. The above composition does not contain substantially VOCs and is easily dispersible in water. Another advantage of this composition is that it reduces or significantly reduces the amount of energy and time required to effect curing.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Although the present invention is particularly applicable to coatings for printing stencils, it should be understood that any coating or substrate application, for printing or non-printing purposes, is within its scope. The percentages of materials are by weight unless manifested otherwise. Note that all quantities listed below will be understood to be modified by the term "approximately" except in the Examples and unless otherwise indicated. The water-curable, water-washable, substantially water-free, water-curable composition herein includes an epoxy oligomer and / or urethane oligomer having at least two polymerizable, ethylenically unsaturated moieties, an alkoxylated polyol monomer that has when minus two ethylenically unsaturated fractions and a surfactant which is copolyzable with the oligomer and / or monomer. An aliphatic and / or aromatic urethane oligomer can be optionally used instead of. or in addition to the epoxy oligomer. The urethane oligomer component is preferably a urethane acrylate such as, for example, PHOTOMER (R) 6008 available from Henkel Corporation. However, the epoxy oligomer is also preferred. Also, the epoxy oligomer can optionally be accompanied by polyester acrylate oligomer, trimethylolpropane dimer ester tetraacrylate oligomer, or dipolyoxypropylene glycerol adipate oligomer. In general, the composition is energy curable of the present invention includes the following percentages by weight of component: Oligomers 30% -70% Monomers 30% -70% 10 Surfactants 0 1% to about 20% Photoimagers 0-10% The epoxy oligomer can be prepared by reacting a epoxide with an unsaturated acid , c such as acrylic or methacrylic acid, optionally in the presence of a polyamide derived from a polymerized fatty acid. In one embodiment, the epoxy acrylate oligomer is derived from a compound having the formula R1- [CH2-CHOH-CH2-0 (0) C-CH = CH2] u wherein R1 is an aliphatic, aromatic or of arene having at least two carbon atoms and at least two oxide residues, and n is an integer of 2 to 6. Useful epoxides include the glycidyl ethers of both polyhydric phenols and polyhydric alcohols, epoxidized fatty acids or oil drying, epoxidized diolefins, epoxidized diunsaturated acid ester, as well as epoxidized unsaturated polyesters, preferably containing an average of more than one epoxide group per molecular. The preferred epoxy compounds will have a molecular weight of 300 to 600 and an epoxy equivalent weight of between 150 and 1200. Representative examples of the epoxides include condensation products of polyphenols and (methyl) epichlorohydrin. For polyphenols, bisphenol A, 2, 2'-bis (-hydroxy phenyl) methane (bisphenol F), halogenated bisphenol A, resormyol, hydroquinone, catechol, tetrahydroxy phenylethane, phenol novolac, cresol novolac, novolac can be listed. Bisphenol A and bisphenol F novolak can also be listed. 15 Epoxy compounds of the alcohol ether type obtainable from polyols such as alkylene glycols and polyalkylene glycols, e.g., ethylene glycol, 1,2-propylene glycol, 1, 3 propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diglycerol, trimethylolpropanol, pentaerythritol, inositol, sorbitol, polyglycol 1 glycol, polypropylene glycol, polytetrahydrofuran, (ie, poly (1,4-butanediol) , which can be obtained under the designation TERATHONE (R) from DuPont), and adduct of alkylene oxide of bisphenols, and 25 (methyl) epichlorohydrin; glycidyl amines that can be ífe süffer - "- 5 ^^^ g ^^^^^^^^^^ g ^^^^^^^^^^ j ^^^^^^^ rfg ^ É" MÍkiL -:,. It is possible to obtain from anilines such as diaminodi phenylmethane, diamofenilsulphone and p-ammophenol, and (me) epichlorohydrin; glycidyl esters based on acid anhydrides such as italic anhydride, and tetrahydro, or hexahydro-ph alic anhydride; and alicyclic epoxides such as 3,4-epoxy-6-methι-cyclohexylmethyl and 3, -epoxy-6-methylcyclohexyl carboxylate. The glycidyl polyols of polyhydric phenols are made from the reaction of a polyhydric phenol with glycerol epihalohydrin or dihalohydrin, and a sufficient amount of caustic alkali to combine with the halogen of the halohydrin. The glycidyl ethers of polyhydric alcohols are made by reacting at least about 2 moles of an epihalohydrin with 1 mole of a polyhydric alcohol such as ethylene glycol, pentaerythritol, etc., followed by dehydrohalogenation. In addition to the polyepoxides made from alcohols or phenols and an epihalohydrin, the polyepoxides made by the known permeation methods are also suitable. The epoxides of unsaturated esters, polyesters, diolefins and the like can be prepared by reacting the unsaturated compound with a peracid. The preparation of polyepoxides by the peracid method is described iá ^^^. 7 ^^. ^. ~ S &!,, .J-jfc -. ^ J-fcMBt - ^^ - ^ > »-.J. In various newspapers and patents and such compounds as butadiene, ethyl linoleate, "as well as di- or tri-unsaturated drying oils or drying oil acids, esters and polyesters can all be converted into polyepoxides The epoxidized drying oils are also well known, these polyepoxides are usually prepared by reaction of a peracid, such as peracetic acid or performic acid with the unsaturated drying oil in accordance with US Patent No. 2,569,502.In certain embodiments, the diepoxide is an epoxidized triglyceride containing unsaturated fatty acids.The epoxidized triglyceride can be produced by epoxidation of one or more triglycerides of vegetable or animal origin.The only requirement is that a substantial percentage of diepoxide compounds must be present. can contain saturated components, however, the glycerol esters epoxides of acid It has an iodine value of 50 to 150 and preferably 85 to 115 are normally used. For example, epoxidized triglycerides containing 2% to 10% by weight epoxide oxygen are suitable. This epoxide oxygen content can be established by using triglycerides with a relatively low iodine value as the starting material and by fully epoxidizing or using triglycerides with a high iodine value as the starting material or only making them partially react with epoxides. Products such as these can be produced from the following fats and oils (listed according to the range of their starting iodine value) beef tallow, palm oil, tallow, castor oil, peanut oil, oil rapeseed and, preferably, cottonseed oil, soy bean oil, train oil, sunflower oil, flaxseed oil Examples of typical epoxidized oils are epoxidized soy bean oil with an epoxide value of 5.8. to 6.5, epoxidized sunflower oil with an epoxide value of 5.6 to 6.6, epoxidized linseed oil with an epoxide value of 8 2 to 8 6, and epoxidized train oil with an epoxide value of 6.3 to 6 7. Examples Additional polyepoxides include diglycidyl ether of diethylene glycol or dipropylene glycol, diglycidyl ether of polypropylene glycols having molecular weight up to, for example, 2,000, glyceryl triglycidyl ether, diglycidyl ether of resorcinol, ethylene glycol. of diglycidyl of 4,4'-isopropylidene phenol, epoxy novolaks, such as the condensation product of 4,4'-methylenediphenol and epichlorohydrin and the condensation of 4,4'-isopropylidene phenol and epichlorhydrin, glycidyl ethers and oil of acajú, epoxidized soy bean oil, epoxidized unsaturated polyesters, vinyl cyclohexene dioxide, dicyclopentadiene dioxide, dipentene dioxide, epoxidized polybutadiene and epoxidized aldehyde condensates such as 3, -epiciclohexyl-methyl-3'- carboxylate 4'-epoxycyclohexane. Particularly preferred epoxides are the glycidyl ethers of isophenols, a class of 10 compounds that consist of a pair of phenolic groups inter-linked through an aliphatic bridge of intervention. While any of the bisphenols can be used, the compound 2, 2-bis (p-hydroxy phenyl) -propane, commonly known as bisphenol A, is more widely available commercially and is preferred. Especially preferred are the liquid Bisphenol A-epichlorohydrin condensates with a molecular weight in the range from 300 to 600. The acid component is comprised of an ethylenically unsaturated acid. The ethylenically unsaturated monocarboxylic acid, particularly suitable are the alpha, beta monobasic acids. -unresaturated. Examples of these monocarboxylic acid monomers include acrylic acid, 2-beta-acryloxypropionic acid, methacrylic acid, acid AJ i ^.,. ^. ^^ fe ^ j ^ s ^^^^^ .- j ^^^^ JfcA =,: ^. ^ = Ska á ^^ A * t crotonic, and acid to fa-chloroacrylic. Preferred examples are acrylic acid and methacrylic acid. Suitable acid components are also adducts of hydroxyalkyl acrylates or hydroxyalkyl methacrylates and the anhydrides of dicarboxylic acids, such as for example, italic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, octenylsuccinic anhydride, dodecenylsuccinic anhydride, chlordened anhydride, anhydride tetrahydrof tálico, hexahidrofálico anhídrido and metiltetrahidrofálicoal anhídrido. These adducts can be prepared by methods of organic chemistry of preparation known in the art. The acid component can also contain other carboxylic acids. In certain embodiments, the acid component will be comprised of a minor amount, e.g., less than 50% of the total acid equivalents, more typically less than 20% of the total acid equivalents, of a fatty acid. The fatty acids are saturated and / or unsaturated aliphatic monocarboxylic acids containing 8 to 24 carbon atoms or saturated or unsaturated hydroxycarboxylic acids containing 8 to 24 carbon atoms. The carboxylic acids and / or hydroxycarboxylic acids may be of natural and / or synthetic origin. Examples of suitable monocarboxylic acids are caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, palargonic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petrosilic acid, linoleic acid, linolenic acid, elaeostearic acid, fatty acid conjune, ricinoleic acid, aracaric acid, gadoleic acid, behenic acid, erucic acid and bradynic acid and the technical mixtures thereof obtained, for example, in the hydrolysis under pressure of natural fats and oils, in the oxidation of aldehydes of the synthesis Roelen oxo, or as a monomeric fraction in the dimepzation of unsaturated fatty acids. In a particularly preferred embodiment, the fatty acid is derived from technical mixtures of the aforementioned fatty acids which can be obtained in the form of technical mixtures typically found in oleochemistry after pressure hydrolysis of oils and fats of animal or vegetable origin , such as coconut oil, palm kernel oil, sunflower oil, rapeseed oil, and coriander oil and beef tallow. However, the fatty acid may also contain a branched fatty acid residue, for example the residue of 2-ethylhexanoic acid, isopalmitic acid or isostearic acid. The preferred fatty acids are mixtures obtained from natural sources, v gr. , palm oil, palm kernel oil, coconut oil, rapeseed oil (from old high erucic acid plants or from new low erucic acid plants, aka 5 oil canola), sunflower oil (from old low oleic plants or from tall new oleic plants), castor oil, soybean oil, cottonseed oil, peanut oil, olive oil, olive skin oil, coriander oil, oil castor oil, prairie foam oil, chaulmoogra oil, tea seed oil, linseed oil, beef tallow, fat, fish oil and the like. Naturally occurring fatty acids are typically present as triglycerides of mixtures of acids Fatty acids, where all the fatty acids have an even number of carbon atoms and a major portion by weight of the acids have from 12 to 18 carbon atoms and are saturated or mono-, di-, or tri-unsaturated. The preferred epoxy resins, that is, those made of bisphenol A, will have two epoxy groups per molecule. In this way, the product of a reaction with acrylic or methacrylic acid will contain an epoxy (meth) acrylate compound) having a polyepoxide backbone and both terminals of a group (meth) acrylate, respectively. Consequently, the The stoichiometric amount of acrylic acid to form a diacrylate adduct would be two moles of acid per two epoxy group. In practice, however, it is preferred to use an amount of acid slightly in excess of the amount necessary to cover both epoxy groups. Therefore, the amount of acrylic acid reacted is typically between 2,001 moles to 2.1 moles, and more typically between 2.01 and 2.05 moles of acid for two epoxy groups. Alternatively, the reaction of the epoxide and the acid may occur in the presence of a polyamide derived from a polymerized fatty acid. The polyamide preferably has a number average molecular weight of less than 10,000 grams / mole. Polyamide resins from Low melting that melt within the apimate scale of 902C to 130aC can be prepared from polymeric fatty acids and aliphatic polyamines. Typical of the polyamines that can be used are ethylenediamine, diethylene triamine, tetylenetetramine, -tetraethylenepentamine, 1,4-diaminobutane, 1,3-diaminobutane, hexamethyldiamine, piperazine, isophorone diamine, 3- (N-isoylamine) -ylamine, 3,3'-iminobisylamine, and the like. A preferred group of these low melting polyamides is derived from polymeric fatty acids, and ethylenediamine and are solid at room temperature Suitable polyamides are commercially available under the trade designation of polyamide reams VERSAMID, v. gr. , VERSAMID 335, 5 750 and 744, and are amber-colored resins having a number average molecular weight of up to 10,000, preferably from 1,000 to 4,000 and a softening point of from below room temperature to 190 ° C. The preferred polyamide is VERSAMID 335 polyamide which is commercially available from Henkel Corporation and has an amine value of 3, a number average molecular weight of 1699, as determined by gel permeation chromatography (GPC) using a polystyrene standard, and a polydispersity of 1 90 The preparation of said VERSAMID polyamide resins is well known and by varying the acid and / or functionality of the polyamine, a wide variety of Viscosities, molecular weights and levels of active amino groups spaced along the resin molecule can be obtained Typically, the VERSAMID polyamide resins useful herein have amine values of 0 to 25, preferably 0 to 10, more preferably 0 to 5 viscosities of apimately 1 to 30 poises (at 160a C) j * ü- and polydispersities of less than 5. The amine value and number average molecular weight of the polyamide can be determined as described in E.U.A. 4,652,492 (Seiner et al.), The disclosure of which is incorporated herein by reference. The polyamide is incorporated into the composition in an amount not exceeding 50% by weight based on the combined weight of the epoxide and acid components and the polyamide. Preferably, an amount not exceeding 25% by weight is used and more preferably is an amount of 5% to 15% by weight. The reaction between the epoxide and acid can be carried out through a wide range of temperatures, v., At 40aC to 150.degree. C., more typically from 50aC to 130aC and preferably between 90aC and 110aC, at atmospheric, subatmospheric or superatmospheric pressure; preferably in an inert atmosphere. The esteri fi cation is continued until an acid number of 2 to 15 is obtained. This reaction usually takes 8 to 15 hours. To prevent premature or undesirable polymerization of the uct or reagents, it is advantageous to add a vinyl inhibitor to the reaction mixture. Suitable vinyl polymerization inhibitors include tert-butylcatechol, hydroquinone, 2, 5-di-tertiary butyl hydroquinone, hydroquinone monoethyl ether, etc. Selling, the ^^^^ 2 ^^! ^^^^ - ^^^^^^^^^^^^^^^^^^^^^ Inhibitor is included in the reaction mixture at a concentration of 0.005 to 0.1 % by weight based on total reagents Reaction between epoxide and acid eeds slowly when not catalyzed, and can be accelerated by suitable catalysts which are preferably used, such as, for example, tertiary bases such as triethylamine, tributylamine, pyridine, dimethylaniline, tris (dimethylaminomethyl) -phenol, triphenyl phosphine, tributyl phosphine, tributyl ethylol; alcoholates such as sodium methylate, sodium butylate, sodium methoxy glycolate, etc.; quaternary compounds such as tetramethyl ammonium bromide, tetramethylammonium chloride, benzyltrimethylammonium chloride, and the like. at least 0.01 percent, based on the total weight of reagents, preferably at least 0.1 percent, of said catalyst is desirable. Typical examples of suitable monomers that can be used and added to the reaction mixture before or during the reaction, or added after the reaction, as a reactive diluent, are vinyl or vinylidene monomers containing ethylonic unsaturation, and can be copolymerized with the compositions of this invention are, styrene, vinyl toluene, tertiary butyl styrene, fa-methyl-styrene, monochlorostyrene, dichlorostyrene, divinylbenzene, ethyl vinyl benzene, diisopropenylbenzene, methylacrylate, ethylacrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, vinyl esters such as vinyl acetate and the monovinyl esters of aliphatic, monobasic and polybasic saturated and unsaturated acids, such as the vinyl esters of the following propionic, caproic, oleic, stearic, acrylic, methacrylic, crotonic acids , succinic, maleic, fumaric, ethiconic hexahydrobenzoic, citric, tartaric, etc., as well as the corresponding allyl, metalyl esters, etc., esters of the aforementioned acids, monoesters and diesters of itaconic acid, such as methyl, ethyl, butyl esters, etc; the monoesters, diesters of maleic and fumaric acid and their amide and nitrile compounds, such as diethylmaleate, maleyl tetramethyldiamide, fumaryl dinitrile, dimethyl fumarate; cyanuric acid derivatives having at least one copolymerizable unsaturated group attached directly or indirectly to the triazine ring such as diallylethyl cyanurate, triallyl cyanurate, etc., ethers such as vinyl allyl ether, divinyl ether, diallyl ether, ether of resorcinol divinyl, etc., diallyl clorendate, diallyl tetrachlorolate diallyl tetrabromoftallate, dibromopropargyl acrylate, as well as the soluble or partial soluble polymeappable polymers of the above listed monomers etc. When preparing the polymerizable compositions containing the reaction product of this invention and one or more of the monomers of the type listed above, the relative amount of the monomers may vary widely In general, however, the monomer or monomers are used at less than 50% by weight of the composition, typically on the scale of about 1% to 30% by weight, and more typically on the scale of 5% to 15% by weight The epoxy oligomers prepared by reacting an epoxide with acrylic acid in the presence of a polyamide derived from a polyepped fatty acid have the advantage of being thixotropic. The viscosity of compositions containing these oligomers decreases with the application of increasing agitation or shear and gradually returns to its previous viscous state when allowed to stand In this way the composition exhibits lower viscosity when it is in the process of being applied to a substrate ba or the application of force or pressure However once the coating has been applied it resumes its viscosity state elevated and tends to remain on the substrate without running. Likewise, the epoxy oligomer can optionally be accompanied by a polyester acrylate oligomer, trimethylolpropane dimer ester tetraacrylate oligomer, or dipolyoxypropylene glycerol adipate oligomer. Referring now to the alkoxylated polyol component of the composition described herein, the preferred alkoxylated polyol monomer has the formula: wherein R2 is an aliphatic, aromatic or arene moiety having at least two carbon atoms and at least two oxide residues Y is a fraction of alkylene oxide and x is an integer from 2 to 6, R3 is hydrogen or -C (0) OR5 wherein R5 is hydrogen or an alkyl group of 1 to 33 carbon atoms, and m is a whole from 2 to 6. More particularly, R2 may be a residue of ethylene glycol, propylene glycol residue, trimethylolpropane residue, pentaerythritol residue, neopentyl glycol residue, glyceryl residue, diglyceryl residue, inositol residue, sorbitol residue, residue of hydroquinone, catechol residue, or bisphenol residue (see bisphenol A). R2 can also be to be selected from straight or branched chain saturated or saturated fractions of 6 to 24 carbon atoms such as epoxidized soy bean oil residue. Alternatively, R2 may be polyethylene glycol or ethylene oxide / propylene oxide copolymer Y is preferably a residue of ethylene oxide or propylene oxide R3 can optionally be for example the linking groups -0-, -0 (0) C-, -OCH2CH2-, or -OCH2CHOHCH20 (O) C- The monomer component of The alkoxylated polyol preferably comprises a mixture of at least one alkoxylated polyol diaclate such as, for example, bisphenol ethoxylate diacrylate and / or neopentyl glycol propoxylate diacrylate, and at least one alkoxylated polyol tpacrylate, such as, for example, ethoxylate triacplate, trimethylolpropane A preferred composition includes 105 to 15% by weight of neopentyl glycol propoxylate diaccolate, 5% to 10% of bisphenol A ethoxylate diaclet and 15% to 20% of Tpmethylolpropane ethoxylate triac ilato based on the weight of the total composition Preferably also, the epoxy oligomer component used in conjunction with the monomer component of * _ IA ^ L .. ^ ......, ...'-. ..... s ^^ a uu ^ ^ Y! ^^ 'alkoxylated polyol is obtained by reacting a diepoxide such as a diglycidyl ether of a dihydric phenol (e.g., bisphenol A) with an unsaturated acid component (e.g., acrylic acid) in the presence of a polyamide derived from a fatty acid With reference now to the surfactant component, the photopolymerizable printing stencil coating pastes are insoluble in water, hence the need for an agent surfactant capable of providing dispersibility in water so that the uncured coating paste can be washed by the application equipment. It is more efficient to include the surfactant as part of the stencil printing ink composition instead of as a component in the wash water. The surfactants described herein are capable of being integrated into the molecular structure of the cured polymer resulting from the copolymerizable oligomer of the alkoxylated polyol monomer components.

The integration of the surfactant into the molecular structure of the cured polymer can be achieved, v. Gr, by covalent bonding. For example, the surfactant may include one or more active sites capable of establishing covalent bonds, such as by For example, unsaturated sites or reactive groups.

Alternatively, the surfactant can be integrated into the molecular structure of the cured polymer by means of hydrogen bonds. In any case, the surfactant has the advantage of not migrating within the cured coating. In addition, the integration of the surfactant prevents the water sensitivity of the cured polymer coating that would be caused by the presence of the free surfactant. A type of surfactant found to be suitable for use in the composition of the present invention includes ethylene oxide / propylene oxide block copolymers. These copolymers are available from BASF Corporation under the designations PLURONIC P105. PLURONICMP F108, PLURONIC "F104, and PLURONICMR L44, for example, and have the following formula: HO- (CH2CH20) a- (CH (CH3) CH20)" - (CH2CH20) CH where b is at least 15 y (CH2CH20) ) a + c is varied from 20% -90% by weight Another type of surfactant suitable for use in the composition of the present invention includes ethoxylated acetyl alcohol and diols such as those available under the designations SURFYNOL (R) 465 and SURFYNOL (R) 485 (W) by Air Products Co. A preferred surfactant includes an acetylenic glycol deceneiol Still another type of surfactant suitable for use in the present invention includes fluoropolymers and prepolymers, such as, for example, fluorinated alkyl esters such as 2-N (alkyl perfluorooctane sulfonamide) ethyl acrylate which is available under the designation FLUORAD FC-430 from 3M Co. Still another type of surfactant suitable for use in the present invention includes epoxy silicones such as SILQUEST A-187 available from OSi Specialties, Inc., of Danbury, Connecticut, having the formulás O H2C-CHCH 2 OCH 2 S 1 (OCH 3) 3 Generally, the surfactant preferably constitutes 0.1% to 20% of the total composition, more preferably from 0.5% to 10% and more preferably from 1% to 5% The polymerization of the energy-polymerizable composition of the present invention can be effected by use, for example, of electron beam radiation (EB) or ultraviolet (UV) radiation 5 Photoinitiators are not a required component of the < - * '• < "", • '*** "" 7 composition if EB radiation is used to effect polymerization, however, if UV radiation is used, the composition should include a photoinitiator, any photoinitiator appropriate for the purposes described in present may be employed Examples of useful photoinitiators include one or more compounds selected from benzyldimethyl ketal, 2,2-diethoxy-1,2-di-phenyletanone, 1-hydroxy-cyclohexyl-phenyl ketone, fa, fa-dimethoxy- to fa-hydroxy acetophenone, l- (4-isopropyl phenyl) -2-hydroxy-2-yl-propan-l-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydrox? -2- methyl-propan-2-one, 2-methyl-l- [4- (methyl thio) phenyl] -butan-1-one, 3, 6-bis (2-met? L-2-mor folino-propanonyl) -9-but-l-carbazole, 4, '-bis (dimethylamino) benzophenone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropyl thioxanthone, 4- isopropyl ioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, 4-benzoyl-N, N-dimethyl-N- [2- (l-oxo-2-propenyl) oxy] ethylbenzene-ammonium chloride, methyldiethanolamine, triethanolamine ethyl 4- (dimethylamino) -benzoate, 2-n-butoxyethyl (methylamino) benzoate and combinations thereof. Benzophenone, which itself is not a photoinitiator, can be used in photoinitiator compositions in conjunction with a coinitiator such as thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, and amine coinitiators such as ildiethanolamine and ethyl 4- (dimethylamino) benzoate. It is preferable to have a mixture of photoinitiators so that the combined absorption spectra of the individual photoinitiators coincide with the spectral output of the UV lamp / or other radiation emitter) used to effect the curing of the coating or ink composition. For example, mercury vapor lamps have strong emissions on the UV scale of 2400 to 2800 A and on the UV scale of 3400 A to 3800 A. By selecting an appropriate mixture of photoinitiators, further use can be achieved 1 5 efficient spectral output of the lamp. This increased efficiency can be translated into faster production during the energy polymerization process. In addition, the coatings that use the The composition described herein may include dyes such as pigments and dyes that absorb UV light. For example, pigments generally absorb light wavelengths less than 3700A. To cure said coating it is necessary to generate free radicals 5 using a photoinitiator that absorbs light above 3700A. A suitable photoinitiator for pigmented systems includes 2-benzyl-2-dimethylamino-1- (4-mor pholinophenyl) -butan-1-one, which is commercially available under the designation Irgacure 369 from Ciba-Geigy to ensure that the composition does not polymerize prematurely, a free radical inhibitor may optionally be added to the polymerizable composition. Examples of suitable inhibitors include hydroquinone and methyl ether thereof or butylated hydroxytoluene at a level of 5 ppm to 2000 ppm by weight of the polymerizable components. additives that are particularly useful for prolonging the shelf life of the composition can also be used, eg, UV stabilizers such as Fluorstab U.V.-II from Kromachem. The UV radiation is preferably applied to a film of the present composition at an energy density of 2,000 to 3,000 mJ / cm2, more preferably 2,200 to 2,500 mJ / cm2, in order to optimize the complete curing of the film. While the film may be tack-free with exposure to 20-40 mJ / cm2, energy densities less than 2000 mJ / cm2 produce a film with a lower degree of crosslinking (as measured by pendulum hardness test), and densities . ,. M: JW,, £ ig of energy greater than 3000 exhibit a detrimental effect on the cured film. The composition described herein can be applied to a screen as a coating in a conventional manner. For example, the composition can be applied to brushes, rollers, spraying or by dipping the stencil into the composition. The stencil can be a mesh made, for example, silk, polyester, polypropylene, high density polyethylene, nylon, glass, and metal such as nickel, aluminum, steel, etc. The coating composition is then cured or hardened by exposure to polymerization radiation such as UV or EB radiation to form a mold stencil. In general, an exposure time of six seconds is sufficient to cure the composition towards a tack-free, hard coating with an energy requirement of 460 kJ per kg. of stencil fabric. After the coating has hardened In the case of stenciling, the mold stencil can be etched, for example by means of laser light, to create porous areas in the shape of the desired marking. The engraved stencils can then be used as a mask in a screen printing process in a conventional manner. The uncured composition that remains in the equipment * • ', ^ jwwh application is easily washable with water. The wettability of the composition described herein on a substrate such as nickel can be measured by contact angle goniometry. The present composition exhibits a contact angle in nickel of not more than 100a, more preferably not more than 702, and more preferably not more than 309. The following examples are provided for the purpose of illustrating the present invention.

EXAMPLE 1 A composition was made by mixing the following components: Oligomer component: 40% of a composition containing an epoxy oligomer obtained by reacting a diglycidyl ether of bisphenol A with acrylic acid in the presence of Versamid polyamide 335 (10%) and propoxylated glycerol triacrylate (15%). 9% dipolyioxypropylene glycerol adipate oligomer. Monomer component: 17% trimethylol propane ethoxylate triacrylate (available from Henkel Corp. under the designation Photomer (4149). - -rr- fi,! nlf-T- • r ^. ,,, »: _ Y» * r ?. «_-» .. ,,.,, -.-¿? "12.5% neopentyl glycol propoxylate diacrylate (available from Henkel 'Corp. under the designation Photomer 4028). Photoinitiator component: 5 mixture at 0.5% of thioxanthone of 2-isopropyl and 4-isopropylthioxanthone (available from International Bio-Synthetics under the designation Quantacure ITX). 2.5% of 2-methyl-l- [4- (methylthiol) phenyl] -2- mor folino-propan-1-one (available from Ciba-Geigy under the designation Irgacure 907). Pigment Compound '0.25% Yellow Irgalite Surfactant Component 12% ethylene oxide / propylene oxide block copolymer (available from BASF under the designation Pluronic F-105.) The above components were mixed in accordance with the following Procedure: First, the epoxy acrylate oligomer, 50% Photomer 4028, all the Photomer 4127, and the pigment were mixed together with grinding to form a ground paste, then the rest of the oligomer components were added to the ground paste The surfactant mixture was prepared by mixing the surfactant 25 with 50% of the Photomer 4149 under gentle heating (less 35eC). The surfactant mixture was then added at room temperature to the ground pulp with stirring. The photoinitiator was mixed with the remaining 50% of Photomer 4149 and then added to the ground paste with mixing. The resulting composition was self emulsifying, had a viscosity of 2300 centipoise, and exhibited thixotropic shear thinning characteristics. The composition was applied to a 2 micron thick film to stencil substrates of aluminum, nickel and steel mesh and then cured by passing the substrates under a U.V. under the following conditions: Lamp: Hg steam Power: 300 watts / cm Conveyor speed: 20 m / min. Exposure time 6 seconds Exposure temperature: 25aC The film was observed to be tack-free after one pass The following tests were performed on the cured film The wettability of the metal substrates by the composition was measured using an angle goniometer. contact at room temperature. The contact angle of the film based on epoxy acrylate ?? ** - And * ^ "^ UV-cured of this Example was found to be 27 5 degrees. The hardness of the cured film, a crosslink density indicator, was measured in accordance with the wetness test of ASTM D4366-92 Pendulum. The cured film exhibited a hardness of 157 beads as measured by this test. The solvent resistance of the cured film was measured by the double rub test of ASTMD D5402-93 MEK The cured film was measured at more than 200 double rubs. The adhesion of the film was determined by a conventional tape test and by scanning electron microscopy. Film 15 exhibited sufficient adhesion.

EXAMPLE 2 A composition was made by mixing the following components: Oligomer Component: 37.35 of an epoxy oligomer-containing composition obtained by reacting a diglycidyl ether of bisphenol A with acrylic acid in the presence of Versamid 335 (10%) polyamide and triacrylate Propoxylated glyceryl (15%).

Monomer component '18.66% trimethylol propane ethoxylate triacrylate (Photomer 4149) 9.33% neopentyl 5 glycol propoxylate diacrylate (Photomer 4127) 13.99% bisphenol-A-ethoxylate diacrylate (Photomer 4028). Photoinitiator component: 9 52% uantacure mixture 369 (available 10 from International Bio Synthetics and Darocur 4265 (available from Merck) Pigment component: 1.87% Irgalite yellow Surfactant component: 9.33% oxide copolymer ethylene / propylene oxide (Pluronic 105 available from BASF) The composition of this Example was prepared according to the mixing method of Example 1. The composition was washable with water. 3500 centipoises and exhibited thixotropic shear thinning characteristics The composition was applied to a nickel stencil substrate and then cured by passing the substrate under a UV lamp under the same conditions as those set forth in Example 1 H.H! % - > - < : '* • «^«? "?," J. ", ^ ..,, ^^ &-jgafc» «* a &?« »= > The sample was observed to be tack-free after one pass. The contact angle measured by a goniometer was an indicator of wettability of 27.5.

EXAMPLE 3 A composition was made by mixing the following components: Oligomer component 40% of an epoxy oligomer-containing composition obtained by reacting a diglycidyl ether of bisphenol A with acrylic acid in the presence of Versamid polyamide 335 (10%) and triacrylate Propoxylated glyceryl (15%). 9% dipolyioxypropylene glycol adipate oligomer. Monomer component: 17% trimethylol propane ethoxylate triacrylate (Photomer 4149). 13% neopentyl glycol propoxylate diacrylate (Photomer 4127) 6% bisphenol-A-ethoxylate diacrylate (Photomer 4028). Photoinitiator component: 3% 2-benzyl-2-N, N-dimethylamino-1- (4- morpholinophenyl) -1-butanone, available as Irgacure 369 1% thioxanthone Pigment component: 1% Ftalo Blue GS 5 Surfactant component 10% ethylene oxide / propylene oxide copolymer (Pluronic 108 available from BASF) The composition of this Example was prepared according to the mixing method of Example 1. The The composition was washable with water and exhibited thixotropic shear thinning characteristics.

EXAMPLE 4 A composition was made by mixing the following components: Oligomer component: 25% of an epoxy oligomer-containing composition obtained by reacting a diglycidyl ether of bisphenol A with acrylic acid in the presence of polyamide Versamid 335 (10%) and triacrylate of propoxylated glyceryl (15%). Monomer component. 27.25% Trimethylolpropane Ethoxylate Triacrylate (Photomer 4149) 8% neopentyl glycol propoxylate diacrylate (Photomer 4127). 30% diacrylate of bisphenol-A-ethoxylate (Photomer 4028) Component of photoinitiator: 2.5% Irgacure 369 0.94% thioxanthone. Pigment component. 0.31% of Blue phthalo GS Component of surfactant. 6% ethylene oxide / propylene oxide copolymer (Pluronic 108 available from BASF). The composition of this Example was prepared according to the mixing method of Example 1. The composition was washable with water and exhibited thixotropic shear thinning characteristics. Even though the previous description contains many specific, these specifics should not be considered as limitations on the scope of the invention, but only as exemplifications of preferred embodiments thereof. Those skilled in the art will see many other possible variations that are within the scope and spirit of the invention as defined by the appended claims hereto.

Claims (1)

1. CLAIMS 1. - A polymer formation composition, energy curable, washable? water, free of water, comprising: a) an oligomer selected from the group consisting of epoxy oligomer and urethane oligomer, the oligomer having at least two ethylenically unsaturated fractions; b) at least one alkoxylated polyol monomer having at least two ethylenically unsaturated moieties and capable of being copolymerized with oligomer component (a) to provide a solid cured polymer when exposed to energy polymerization conditions; and, c) at least one surfactant capable of being integrated into the molecular structure of the polymer resulting from the copolymerization of (a) and (b) either by covalent bond and by hydrogen bonding, and further capable of making the water dispersible composition 2 - The composition according to claim 1, wherein the epoxy oligomer is an epoxy acrylate oligomer. '&3 3. The composition according to claim 2, wherein the epoxy acrylate oligomer is derived from a compound having the formula: R1- [-CH2-CHOH-CH2-0 (O) C-CH = CH2] "wherein R1 is an aliphatic, aromatic or arene moiety having at least two carbon atoms and at least two oxide residues, and n is an integer from 2 to about 6. 4.- The composition according to claim 3, wherein R1 is a bisphenol residue 5. The composition according to claim 3, wherein R1 is selected from the group consisting of hydroquinone residue and catechol residue 6 - The composition according to claim 3, wherein R1 includes a straight or branched chain alkyl group of 2 to about 6 carbon atoms. 7. The composition according to claim 6, wherein R1 is selected from the group consisting of ethylene glycol residue, propylene glycol residue, trimethylolpropane residue, pentaerythritol residue, neopent glycol residue, glyceryl residue, diglyceryl residue, inositol residue, and 3% < SSS * i sorbitol residue. 8. The composition according to claim 3, wherein R1 is a straight or branched chain, saturated or unsaturated aliphatic fraction of about 6 to about 24 carbon atoms. 9. The composition according to claim 8, wherein R1 is a residue of epoxidized soybean oil. 10 - The composition in accordance with the 1 claim 3, wherein R1 is a polyethylene glycol fraction. 11. The composition according to claim 3, wherein R1 is a copolymer of ethylene oxide-propylene oxide 12. The composition according to claim 1, wherein the epoxy oligomer is thixotropic. 13. The composition according to claim 1, wherein the epoxy oligomer is obtained 20 reacting a diepoxide with an acidic component having an ethylenically unsaturated carboxylic acid or reactive derivative thereof in the presence of a polyamide derived from a polymerized fatty acid. 25 14.- The composition in accordance with the CwSÍfc¿-¿. ' - n. . '•' • -. ' < Mr- -, .; »* ^^^ fef-AáJSáx aáa. claim 13, wherein the acid component is acrylic acid 15. The composition according to claim 14, wherein the diepoxide is a diglycidyl ether of a dihydric phenol. 16 - The composition according to claim 1, wherein the alkoxylated polyol monomer has the formula: R2- [- (Y) * - R3-CH = CH-R4] "wherein R1 is an aliphatic, aromatic or arene, which has at least two carbon atoms and at least two oxide residues, Y is a fraction of alkylene oxide and x is an integer from 2 to about 6, R3 is a linking group capable of binding the oxide fraction Y of alkylene and the group -CH = CH-, R4 is hydrogen or -C (0) OR5 wherein R5 is hydrogen or an alkyl group having from 1 to about 22 carbon atoms, and n is an integer from 2 to about 6 17. The composition according to claim 16, wherein R2 is a bisphenol residue 18- the composition according to claim 16, wherein R2 is selected from the group consisting of hydroquinone residue and catechol residue 19 - The composition in accordance with • f¡ ** ~ < s-? fc € X ^ ñ & a. Claim 16 wherein R2 includes a straight or branched chain alkyl group of 2 to about 6 carbon atoms. The composition according to claim 16 wherein R2 is selected from the group consisting of ethylene glycol residue, propylene glycol tpmethylolpropane residue pentaeptptol residue neopent glycol residue, glyceryl residue digliceplo residue, inositol residue and sorbitol residue 21 - The composition according to claim 16 wherein R2 is a straight or branched chain aliphatic fraction, saturated or msaturated from about 6 to about 24 carbon atoms 22 - The composition according to claim 16 wherein R2 is a residue of epoxidized soy bean oil 23 - The composition according to claim 16 wherein R2 is a polyethylene glycol fraction 24 - The composition according to claim 16 wherein R2 is a copolymer of ethylene oxide-propylene oxide 25 - The composition according to claim 16, wherein Y is an oxide residue of *? "1SzX'- * < *. Y 7. - > M" «S ñi et full 26.- The composition according to claim 16, wherein R3 is a member selected from the group consisting of in -0-, -0 (0) C-, -OCH2CH2- and -OCH2CHOHCH20 (O) C- 27 - The composition according to claim 16, wherein the at least one alkoxylated polyol monomer comprises a mixture of at least one alkoxylated polyol diacrylate and at least one alkoxylated polyol t-plate. 28. The composition according to claim 27, wherein the composition exhibits a contact angle on nickel of no more than about 100 to 29.- The composition according to claim 27, wherein the composition exhibits a contact angle. on nickel of not more than about 70a 30.- The composition according to claim 27, wherein the composition exhibits a contact angle on nickel of no more than about 30a. 31. The composition according to claim 27, wherein the composition includes from about 5% to about 30% of the at least one Figure imgf000018_0001 of the at least one alkoxylated polyol diacrylate and from about 5% to about 305 of at least one alkoxylated polyol triacrylate, based on the total weight of the composition. 32. The composition according to claim 2, wherein the composition includes from about 10% to about 25% of at least one alkoxylated polyol diacrylate and from about 10% to about 25% by weight of at least one The alkoxylated polyol triacrylate is based on the total weight of the composition. 33. The composition according to claim 27, wherein the composition includes from about 15% to about 20% of the at least 15 an alkoxylated polyol diacrylate and from about 15% to 20% of at least one alkoxylated triacrylate based on the total weight of the composition. 34. The composition according to claim 27, wherein the at least one The alkoxylated polyol triacrylate is trimethylolpropane ethoxylate triacrylate and the at least one alkoxylated polyol diacrylate is a member selected from the group consisting of bisphenol A, ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate and mixtures thereof. 35. The composition according to claim 34, wherein the epoxy oligomer is derived from bisphenol A epoxy diacrylate. The composition according to claim 34, wherein the monomer mixture includes about 10% to about 15% by weight of neopentyl glycol propoxylate diacrylate, and from about 15% to about 20% by weight of trimethylolpropane ethoxylate triacrylate, based on 10 the total weight of the composition. 37.- The composition according to claim 36, wherein the monomer mixture further includes from about 5% to about 10% bisphenol A ethoxylate diacrylate. The composition according to claim 36, wherein the epoxy oligomer is obtained by reacting a diepoxide with an acidic component having an ethylenically unsaturated carboxylic acid or reagent derived therefrom in the presence of a polyamide derived from a polymerized fatty acid. 39.- The composition according to claim 38, wherein the acid component is acrylic acid. 25 40.- The composition in accordance with the & * - g ~ ». ^^ ** * * «, *% ES '". E *: ¡^ - ^^ ¿¿¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡ Dihydric 41. The composition according to claim 1, wherein the surfactant includes a block copolymer of ethylene oxide / propylene oxide 42. The composition according to claim 1, wherein the surfactant has at least one unsaturated site, the surfactant 10 being integrated into the molecular structure of the polymer by covalent bonding. 43 - The composition according to claim 42, wherein the surfactant includes a compound having at least one bond 15 acetylenic. 44. The composition according to claim 1, wherein the surfactant includes a diol of acetyl glycol decene. 45.- The composition according to claim 1, wherein the surfactant includes a fluorinated alkyl ester. 46. The composition according to claim 1, wherein the surfactant includes 2-N (alkyl perfluoro octane sul fonamid) ethyl acrylate. 25 47 - The composition in accordance with M iteSifc ^^ claim 1, wherein the surfactant includes an epoxy silicone. 48. The composition according to claim 47, wherein the epoxy silicone includes a compound having the formula: O H2C-CHCH 2 OCH 2 Si (OCH 3) 3 49. The composition according to claim 1, further including a photoinitiator. . 50.- The composition according to claim 49, wherein the photoinitiator is at least one member selected from the group consisting of benzyldimethyl ketal, 2,2-diethoxy-l, 2-diphenyletanone, 1-hydroxy-cyclohexyl. -feni Icetona, al fa, to fa-dimethoxy-to-fa-hydroxy acetophenone, l- (4-isopropyl phenyl) -2-hydroxy-2-methyl-propan-l-one, l- [4- (2-hydroxyethoxy ) phenyl] -2-morpholino-propan-l-one, 2-benzyl-2-N, Nd? methylamino-l- (4-morpholinopheni 1) -butan-1-one, 3,6-bis (2-methyl) -2-morpholino-propanon? L) -9-butyl-carbazole, 4,4'-bis (dimethylamino) benzophenone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 4-isopropyl ioxanone, 2 , 4-dimethylthioxanthone, 2,4-diethyl thioxanthone, 4-benzoyl-N, N-dimethyl-N- [2- (l-oxo-2-propenyl) oxy] -ethylbenzene-ammonium chloride, methyldiethanolamine. triethanolamine, ethyl 4- (dimethylamino) benzoate, 2- (n-butoxyethyl) 4- (dimethylamino) benzoate and combinations thereof. 51. The composition according to claim 1, further including a dye 52.- The composition according to claim 51, wherein the dye is a blue pigment and the composition further includes 2-benzyl-2-N, N-d-methylamino-1- (4-morpholinophenyl) -l-butanone and thioxanthone. 53. The composition according to claim 1, wherein the urethane oligomer is at least one member selected from the group consisting of aliphatic urethane acrylate oligomer and aromatic urethane acrylate oligomer. 54 - A photopolymerized resin obtained by the energy polymerization of the composition according to claim 1. 55.- A stencil coated with a coating material comprising: a) an oligomer selected from the group consisting of epoxy oligomer and urethane oligomer, the oligomer having at least two ethylenically unsaturated fractions; b) at least one alkoxylated polyol monomer having at least two ethylenically unsaturated fractions and capable of being copolymerized with the oligomer component (a) to provide a solid cured polymer when exposed to polymerization conditions with energy; and, c) at least one surfactant capable of being integrated into the molecular structure of the polymer resulting from the copolymerization of (a) and (b) either by covalent bonding or by hydrogen bonding, and also capable of making the composition dispersible in water. 56 - Stencil according to claim 55, wherein the stencil is manufactured from a material selected from the group consisting of silk, polyester, polypropylene, high density polyethylene, nylon, glass, nickel, aluminum and steel 57. - Stencil according to claim 55, wherein the coating material further comprises a photoinitiator. 58 - The stencil according to claim 55, wherein the epoxy oligomer is an epoxy acrylate oligomer derived from a compound having the formula 'R1- [-CH2-CHOH-CH2-0 (O) C-CH2 = CH2 ] " -. & T-iX wherein R1 is an aliphatic, aromatic or arene moiety having at least two carbon atoms and at least two oxide residues and n is an integer from 2 to about 6. 59. The stencil according to claim 55 , wherein the epoxy oligomer is obtained by reacting a diepoxide with an acid component having an ethylenically unsaturated carboxylic acid or reactive derivative thereof in the presence of a polyamide derived from a polymerized fatty acid. 60. The stencil according to claim 55, wherein the alkoxylated polyol monomer has the formula: R2 - [- (Y) x -R3-CH = CH-R4] m wherein R2 is an aliphatic, aromatic moiety or arene having at least two carbon atoms and at least two oxide residues, Y is a fraction of alkylene oxide and x is an integer from 2 to 6, R3 is a linking group capable of binding the Y fraction of oxide of alkylene and the group -CH = CH-, R4 is hydrogen or -C (0) ORs wherein R5 is hydrogen or an alkyl group of 1 to 22 carbon atoms, and m is an integer from 2 to 6. 61.- The Stencil according to claim 60, wherein R2 is selected from the group consisting of bisphenol residue, ethylene glycol residue, propylene glycol residue, trimethylolpropane residue, pentaeptritol residue neopent glycol residue, glyceropyl residue, diglyceryl, mositol residue, and sorbitol residue 62 - Stenciling in accordance with the Claim 55 wherein the coating material is cured 63 - Stencil according to claim 62, wherein the stencil is etched with markings 64 - In a method for coating a substrate wherein the polymer forming composition curable with energy is applied by applying means to a substrate and the polymer formation composition is then exposed to an energy source under conditions such as to form a cured polymer coating on the substrate, an improvement comprising a) employing the applicator means for applying a water-curable, water-curable, water-washable composition substantially free of water comprising an epoxy oligomer having at least two ethylenically unsaturated moieties, ii. at least one alkoxylated polyol monomer having at least two ethylenically unsaturated moieties and capable of being copolymerized with epoxy oligomer (a) to provide a solid polymer when exposed to energy curing conditions, and iii. at least one surfactant capable of being integrated into the molecular structure of the polymer resulting from the copolymerization of (a) and (b) either by covalent bonding or hydrogen bonding, and further capable of making the composition dispersible in water; and, b) washing the applicator means with water to remove the excess polymer formation composition therefrom. The method according to claim 64, wherein the epoxy oligomer is an epoxy acrylate oligomer. 66. The method according to claim 65, wherein the epoxy acrylate oligomer is derived from a compound having the - - '^ Y y-: y' 7Y¿Y '- - "-' '" Y "' Y- - 'formula R2- [- (Y)!, - R3-CH = CH-R4] B in where R1 is an aliphatic, aromatic or arene moiety having at least two carbon atoms and at least two oxide residues, Y is an alkylene oxide moiety and x is an integer from 2 to about 6, R3 is a group of bond able to bind the alkylene oxide fraction Y and the group -CH = CH-, R4 is hydrogen or -C (0) OR5 wherein R5 is hydrogen or an alkyl group having from 1 to about 22 carbon atoms. carbon, and n is an integer from 2 to about 6 - The method according to claim 72, wherein the at least one alkoxylated polyol monomer comprises a mixture of at least one alkoxylated polyol diacrate and at least one tpacrylate. Alkoxylated polyol 74 - The method according to claim 64, wherein the surfactant possesses at least one saturated site, the surfactant 20 being integrated into the molecular structure of the polymer by covalent bond 75 - The method according to claim 74, wherein the surfactant includes a compound having at least one acetylenic bond ¡¡¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿¿? ** ? - ^. * j * > áat & s ~ * & .. & e-e &1 & amp; .J & - - ^ * '& - ** -a & * 2. 76. The method according to claim 64, wherein the surfactant includes an acetylene glycol decene diol 77. The method according to claim 64, wherein the surfactant includes fluorinated alkyl ester. The method according to claim 64, wherein the surfactant includes 2-N acrylate (alkyl? perfluoro octane sulfonamide (ethyl) 79- The method according to claim 64, wherein the surfactant includes an epoxy silicone. 80 - The method according to claim 79, wherein the epoxy silicone includes a compound having the formula O H2C-CHCH2OCH2Si (OCH3) 3 81 - The method according to claim 64, wherein the polymer formation composition further includes a photoinitiator 82 - The method according to claim 64, wherein the polymer forming composition further includes a colorant 83 - E The method according to claim 64, wherein the step of employing the applicator means for applying the polymer-forming composition comprises a method selected from the group consisting of dipping, brushing, spraying or roller-coating. according to claim 64, wherein the substrate is a porous stencil which, with the cured polymer coating provides a mold stencil. The method according to claim 84, further comprising the step of engraving the mold stencil to form a printing mask 86. The method according to claim 85, wherein the etching step is performed by means of of a laser. 87 - The method according to claim 64, wherein the energy source includes electronic beam radiation. 88. The method according to claim 64, wherein the energy source includes UV radiation. The method according to claim 88, wherein the source of UV radiation provides a UV radiation energy density of about 2000 to about 3000 mJ / cm2. The method according to claim 64, wherein the substrate is metal 91 - The method according to claim 64, wherein the substrate is a textile