MXPA00004240A

MXPA00004240A - Inkjet printing medium comprising crosslinked printing surface

Info

Publication number: MXPA00004240A
Application number: MXPA/A/2000/004240A
Authority: MX
Inventors: Huawen Li; Alan E Wang; Charles T Hill; Robert Swisher; David A Diehl
Original assignee: Ppg Industries Ohio Inc
Priority date: 1997-10-28
Filing date: 2000-05-02
Publication date: 2001-05-17

Abstract

An article comprises:(a) a substrate having at least one surface;(b) an interior water-absorptive coating on the surface wherein the interior water-absorptive coating comprises hydrophilic organic polymer which is substantially free from crosslinks derived from ethylenic unsaturation or which contains few crosslinks derived from ethylenic unsaturation;and (c) an exterior water-absorptive coating on the interior water-absorptive coating wherein the exterior water-absorptive coating comprises hydrophilic organic polymer which contains numerous crosslinks derived from ethylenic unsaturation;wherein:(d) the interior coating, the exterior coating, or each of the interior coating and the exterior coating further comprises discrete particles having a number average particle size in the range of from 1 to 500 nanometers.

Description

MEDIA PRINTING BY INK JET THAT CONTAINS AN INTERRUPTED PRINT SURFACE The low resistance to moisture stains is a considerable problem that has arisen in inkjet printing. "Moisture stain resistance" is the ability of inkjet printing to resist stain production when rubbing inkjet substrates and dry in the presence of water. We have now discovered print media that can be printed by ink jet to obtain images of better resistance to moisture stains when used with. a wide variety of inks for inkjet printing, a printed medium that pioporcicna images of better resistance to stains by moisture and a method to produce such products. Accordingly, an embodiment of the invention is a method comprising: (a) providing a substrate having at least one surface; (b) forming an interior coating on the surface by applying to the surface an interior coating composition consisting of: (1) a first volatile aqueous liquid and (2) an organic hydrophilic film-forming polymer solubilized in water or dispersed in water that is substantially free of ethylenically unsaturated groups or containing only a few ethylenically unsaturated groups; (c) forming an outer coating on the inner coating by applying to the inner coating an outer coating composition consisting of: (1) a second volatile aqueous liquid and (2) a film-forming member selected from the group consisting of (A) a hydrophilic organic film-forming polymer solubilized in water containing numerous ethylenically unsaturated groups, (B) an organic hydrophilic film-forming polymer dispersed in water containing numerous ethylenically unsaturated groups, (C) an organic hydrophilic oligomer water-solubilized film former containing numerous ethylenically unsaturated groups, (D) a water-dispersed hydrophilic organic film-forming oligomer containing numerous ethylenically unsaturated groups, (E) a water-soluble hydrophilic organic film-forming monomer containing numerous groups ethylenically unsaturated, (F) a monomer organic hydrophilic film-forming agent dispersed in water containing numerous ethylenically unsaturated groups and (G) a mixture of two or more of these; and (d) exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous crosslinks derived from the ethylenically unsaturated groups present in the applied outer coating composition; wherein: (e) the interior coating composition, the exterior coating composition or each of the interior coating composition and the outer coating composition contain discrete particles that are not film forming and have a numerical average size of particle in the range of 1 to 500 nanometers; (f) the first volatile aqueous liquid is removed from the inner lining to produce an inner liner that abblows water on the surface of the substrate, and (g) the second volatile aqueous liquid is removed from the outer lining to produce an outer lining that absorbs water. -be water on the surface of the inner lining that absorbs water. Another embodiment of the invention is the product produced by the above process. Yet another embodiment of the invention is an article consisting of: (a) a substrate having at least one surface; (b) an interior water-absorbent coating on the surface, wherein the water-absorbent interior coating consists of an organic hydrophilic polymer that is substantially free of cross-links derived from ethylenic unsaturation or that contains a few cross-links derived from ethylenic unsaturation, and (c) ) a water-absorbing outer coating on the water-absorbing inner lining, where the outer water-absorbing coating consists of a hydrophilic organic polymer containing numerous cross-links derived from erillenic unsaturation.; wherein: (d) the inner lining, the outer lining or each of the inner lining and the outer lining further contain discrete particles having a number average particle size in the range of 1 to 500 nanometers. The water absorbing inner liner and the water absorbing outer liner both contain a hydrophilic organic polymer. The difference is that the hydrophilic organic polymer of the water-absorbing inner coating contains a few, if any, cross-links derived from ethylenic unsaturation, while the organic hydrophilic polymer of the second binder contains numerous cross-links derived from ethylenic unsaturation. Crosslinks derived from ethylenic unsaturation can be achieved by re-acting a linear polymer containing a plurality of ethylenically unsaturated groups along the polymeric backbone with a monomer containing at least one ethylenically unsaturated group. Preferably, however, the crosslinkings derived from ethylenic unsaturation are obtained from a polymer, oligomer and / or monomer containing at least two ethylenically unsaturated groups. The water absorbency of the water absorbing inner lining is greater than that of the water absorbing outer lining. The crosslinks in the water absorbent coatings serve to reduce the water solubility of the organic polymer, but also tend to reduce the water absorbency of the coating. The crosslinks present in the water-absorbing outer coating improve the moisture stain resistance of the printing medium, but are not so numerous as to prevent water absorption of the applied ink jet printing ink or the transfer of said water to the water absorbing inner liner. The crossings in the water-absorbing outer coating should also not be so numerous that the time required to dry the ink on the surface of the coating is unduly prolonged. The crosslinks in the water-absorbent interior lining, if present at all, need not be so numerous as to unduly reduce the rate of transfer of water from the water-absorbing outer coating to the water-absorbing interior lining. The organic polymer containing crosslinks may be a single polymer, but is more often a mixture of two or more polymers, at least one of which contains crosslinks. It is possible, but not necessary, that all polymers in a polymer mixture contain crosslinks. The number of crosslinkings derived from ethylenic unsaturation is mainly determined by the number of ethylenically unsaturated groups present in the organic polymer, organic oligomer and / or organic monomer present in the coating composition that is applied to form the coating. In order to be brief, reference will be made to the coating composition used to form the water absorbent interior coating as the "interior coating composition" and reference will be made to the coating composition used to form the water absorbent outer coating as the "exterior cladding com position". Because inter-crossover changes the structure of the monomers, remove them and polymers, the hydrophilic organic polymer present in the water-absorbing inner liner and the hydrophilic organic polymer present in the outer water-absorbing coating are better. described in relation to the polymers, oligomers and / or hydrophilic monomers present in the coating compositions used to form these coatings. The number-average particle size of the discrete particles is between 1 and 500 nanometers. Frequently, the number average particle size is in the range of 1 to 100 nanometers. Frequently, the number average particle size is in the range of 1 to 50 nanometers. Preferably, the number average particle size is in the range of 1 to 20 nanometers. As used herein and in the claims, the average particle size is determined by transmission electron microscopy. The discrete particles can be inorganic filler particles, thermoset organic particles or thermoplastic organic polymer particles substantially non-film forming. The discrete inorganic filler particles that may be present are often discrete metal oxide particles. The metal oxide constituting the particles can be a simple metal oxide (that is, the oxide of a single metal) or it can be a complex metal oxide (i.e., the oxide of two or more metals). The metal oxide particles may be particles of a single metal oxide or may be a mixture of different particles of different metal oxides. Examples of suitable metal oxides include alumina, silica and titania. Other examples of suitable metal oxides include cerium oxide, tin oxide and zinc oxide. Other oxides may optionally be present in a smaller amount. Examples of such optional oxides include, but are not limited to, zirconia, hafia and yttria. Still other metal oxides which may possibly be present are those which are ordinarily present as impurities, such as, for example, iron oxide. For the purposes of the present description and claims, silicon is considered to be a metal. When the discrete particles are alumina particles, more frequently the alumina is alumina monohydroxide. The alumina monohydroxide particles, A10 (OH), and their preparation are known. The preparation and properties of alumina monohydroxide are described by B.E. Yoldas in The American Ceramic Society Bulletin, Vol. 54, No. 3 (March, 1975), pages 289-290; in Journal of Applied Chemical Biotechnology, Vol. 23 (1973), pages 803-809, and in Journal of Materials Science, Vol. 10 (1975), pages 1856-1860. Briefly, aluminum isoprcphoxide or secondary aluminum butoxide is hydrolysed in an excess of water with vigorous stirring at a temperature of 75 to 80 ° C to form a suspension of aluminum monohydroxide. The aluminum monohydroxide is then peptized at temperatures of at least 80 ° C with an acid to form a transparent alumina monohydroxide sol, which exhibits the Tyndall effect when illuminated with a narrow beam of light. As the alumina monohydroxide of the sol is not white or colored, it is not a pigment and does not function as a pigment in the present invention. The acid used does not complex with aluminum and has sufficient strength to produce the required loading effect at low concentration. Nitric acid, hydrochloric acid, perchloric acid, acetic acid, chloroacetic acid, formic acid and methacrylic acid meet these requirements. The acid concentration is usually in the range of 0.03 to 0.1 mole of acid per mole of aluminum alkoxide. Although there is no desire for inclination for any theory, it is believed that the alumina monohydroxide produced in this way is pseudoboehmite. The pseudoboehmite is truly the preferred alumina monohydroxide for use in the present invention. The alumina monohydroxide is not a pigment and does not function as a pigment in the present invention. In most cases, the alumina monohydroxide is clear and colorless. Colloidal silica is also known. Its preparation and properties are described by R.K. Iler in The Chemistry of Silica, John Wiley & Sons, Inc., New York (1979), ISBN 0-471-02404-X, pages 312-337, and in U.S. Patent Nos. 2,601,235, 2,614,993, 2,614,994, 2,617,995, 2,631. 134, 2,885,366 and 2,951,044, the descriptions of which are hereby incorporated by reference in their entirety. Examples of commercial colloidal silica include the colloidal silica Ludox® HS, LS, SM, TM and CL-X (du Pont de Nemours &Company, Inc.), wherein the counter ion is the sodium ion, and the colloidal silica Ludox® AS (du Pont de Nemours &Company, Inc.), in which the counter ion is the ammonium ion. Another example is the colloidal silica Ludox® AM (E.l. du Pont de Nemours &Company, Inc.), in which some of the silicon atoms have been replaced by aluminum atoms and the counter ion is the sodium ion. Colloidal titania is also known. Their preparation and properties are described in U.S. Patent No. 4,275,118. The colloidal titania can also be prepared by the reaction of titanium isopropoxide [CAS 546-68-9] with water and tetramethylammonium hydroxide. The discrete thermosetting organic filler particles that may be present are organic polymer particles crosslinked at least to a degree where they can not be softened or remelted significantly by heat. The thermosetting organic filler particles are not film-forming. Examples of such thermosettable organic polymer particles include melamine-aldehyde thermoset polymer particles, resorcinol-aldehyde thermoset polymer, phenol-resorcinol-aldehyde thermoset polymer, (meth) acrylate thermostable polymer or styrene-thermoset polymer divinylbenzene. The discrete thermoplastic organic filler particles that may be present are thermoplastic in that they can soften and / or melt at elevated temperatures. However, they are not film formers when used according to this invention. Examples of suitable discrete thermoplastic organic polymer particles include polyethylene particles, such as those contained in the Poly-Emulsion 316N30 sol (ChemCor Inc., Chester, NY), maleated polypropylene particles such as those contained in the Poly-Emulsion sol. 43C30 (ChemCor Inc., Chester, NY) and polyacrylate, polymethacrylate, polystyrene and / or fluoropolymer particles made by microemulsion processes. When discrete particles that are not film-forming and having a number average particle size in the range of 1 to 500 nanometers are present in both the interior coating composition and the outer coating composition, they may be the same or different. Similarly, the number average particle size of the non-film-forming discrete particles present in the intercoat coating composition may be the same as or different from the number average particle size of the discrete non-film-forming particles present in the composition. of exterior cladding. The amount of the discrete film-forming particles inside the water absorbing inner liner or in the water-absorbing outer lining, as the case may be, can vary widely. Normally, discrete non-film forming particles constitute from 1 to 80 weight percent of the coating. In many cases, discrete non-film forming particles constitute 5 to 75 weight percent of the coating. 15 to 65 weight percent is preferred. Each of the coating compositions used to produce the printing media of the invention can be independently in the form of an aqueous solution, in which case the volatile aqueous liquid is a volatile aqueous solvent for the organic film-forming polymer of the The coating composition, or the coating composition may be in the form of an aqueous dispersion, in which case the volatile aqueous liquid is a liquid volatile aqueous dispersion for at least part of the organic film-forming polymer of the coating composition. The volatile aqueous liquid is predominantly water. Small amounts of volatile and low-boiling water miscible organic liquids can be intentionally added for particular purposes. Examples of such volatile, low-boiling water-miscible organic liquid water solvents include methanol [CAS 67-56-1], ethanol [CAS 64-17-5], 1-propanol [CAS 71-23-8] , 2-propanol [CAS 67-63-0], 2-butanol [CAS 78-92-2], 2-methyl-2-propanol [CAS 75-65-0], 2-propancna [CAS 67-64- 1] and 2-butanone [CAS 78-93-3]. The list of such liquids is by no means exhaustive. Similarly, miscible organic liquids may be added intentionally in water which are, in themselves, of low, moderate or even insignificant volatility for particular purposes, such as, for example, the delay in evaporation. Examples of such organic liquids include 2-methyl-1-propanol [CAS 78-83-1], 1-butanol [CAS 71-36-3], 1,2-ethanediol [CAS 107-21-1] and 1,2,3-propanetriol [CAS 56-81-5]. The list of such liquids is by no means exhaustive.

Those materials which, although not intentionally added for any particular purpose, are normally present as impurities in one or more of the components of the coating compositions of the invention and which become components of the volatile aqueous liquid, may be present in low concentrations. In most cases, the water constitutes at least 60 percent by weight of the volatile aqueous liquid. Frequently, the water constitutes at least 80 percent by weight of the volatile aqueous liquid. Preferably, the water constitutes substantially all of the volatile aqueous liquid. The amount of volatile aqueous liquid present in the coating composition can vary widely. The minimum amount is that which produces a coating composition with a viscosity low enough to be applied as a coating. The maximum amount is not governed by any theory, but by practical considerations, such as the cost of the volatile aqueous liquid, the minimum desired thickness of the coating to be deposited and the cost and time required to remove the volatile aqueous liquid from the wet coating applied. Normally, however, the volatile aqueous liquid constitutes 30 to 98 weight percent of the coating composition. In many cases, the volatile aqueous liquid constitutes 50 to 96 weight percent of the coating composition. Frequently, the volatile aqueous liquid constitutes from 60 to 95 percent by weight of the coating composition. Preferably, the volatile aqueous liquid constitutes from 80 to 95 percent by weight of the composition. In general, the hydrophilic organic film-forming polymers, the hydrophilic organic film-forming oligomers and / or the hydrophilic organic film-forming monomers present in the coating compositions as film-forming members are water-soluble or water-dispersible. The water-soluble hydrophilic organic film-forming polymers that can be used in the present invention are numerous and widely varied. Examples include poly (ethylene oxide), poly (vinyl alcohol), poly (vinylpyrrolidone), water-soluble cellulosic organic polymer or a mixture of two or more of these. The water-soluble poly (ethylene oxide) is known. Such materials are ordinarily formed by polymerization of ethylene oxide [CAS 75-21-8], usually in the presence of a small amount of an initiator, such as low molecular weight glycol or triol. Examples of such initiators include ethylene glycol [CAS 107-21-1], diethylene glycol [CAS 111-46-6], triethylene glycol [CAS 112-27-6], tetraethylene glycol [CAS 112-60-7], propylene glycol [CAS 57-55-6], trimethylene glycol [CAS 504-63-2], dipropylene glycol [CAS 110-98-5], glycerol [CAS 56-81-5], "trimethylolpropane [CAS 77-99-6] already,? -diaminopoly (propylene glycol) [CAS 9046-10-0] One or more other lower alkylene oxides may also be used, such as propylene oxide [CAS 75-56-9] and trimethylene oxide [CAS 503-30 -0] as a comonomer with ethylene oxide, either to form random polymers or block polymers, but they should be used only in small amounts that do not make the resulting polymer insoluble in water and not dispersible in water. used herein and in the claims, the term "poly (ethylene oxide)" is intended to include the above copolymers of ethylene oxide with small amounts of alkylene oxide lower, as well as ethylene oxide homopolymers. The configuration of the poly (ethylene oxide) may be linear, branched, honeycomb or star-shaped. The preferred terminal groups of the poly (ethylene oxide) are hydroxyl groups, but lower alkoxy end groups, such as methoxy groups, may be present, provided that their type and number do not render the poly (ethylene oxide) polymer Inadequate for its purpose. In most cases, poly (ethylene oxide) is water-soluble. The preferred poly (ethylene oxide) is a water-soluble hsmopolymer of ethylene oxide produced using a small amount of ethylene glycol as an initiator.

The weight-average molecular weight of the water-soluble poly (ethylene oxide) can vary widely. Normally, it is in the range of 100,000 to 3,000,000, although weighted average molecular weights of less than 100,000 or somewhat greater than 3,000,000 can be used. Often, the weight-average molecular weight of the water-soluble poly (ethylene oxide) is in the range of 150,000 to 1,000,000. Frequently, the weight-average molecular weight of the water-soluble poly (ethylene oxide) is in the range of 200,000 to 1,000,000. It is preferred from 300,000 to 700,000. Water-soluble polyvinyl alcohol can be broadly classified as one of two types. The first type is hydrosoluble hydrosoluble poly (vinyl alcohol), in which less than 1.5 mole percent of the acetate groups remain in the molecule. The second type is partially hydrolysed water-soluble poly (vinyl alcohol), in which from 1.5 to even 20 mole percent acetate groups remain in the molecule. The water-soluble organic polymer can include any of the types or a mixture of both. The weight-average molecular weight of the water-soluble poly (vinyl alcohol) can vary considerably, but is frequently in the range of 10,000 to 800,000. In many cases, the weight average molecular weight is in the range of 50,000 to 700,000. It is preferred from 100,000 to 500,000. The water-soluble poly (vinylpyrrolidone) is a known material and can be used. Normally, but not necessarily, the weight average molecular weight of the poly (vinylpyrrolidone) is in the range of 1,000 to 3,000,000. Frequently the weight average molecular weight is in the range of 5,000 to 1,000,000. It is preferred from 5,000 to 500,000.

There are many types that can vary widely from water-soluble cellulosic organic polymers that can be employed in the present invention. Of these, the water-soluble cellulose ethers are preferred water-soluble cellulosic organic polymers. Many of the water-soluble cellulose ethers are also excellent agents for water retention. Examples of the water-soluble cellulose ethers include water-soluble methylcellulose [CAS 9004-67-5], water-soluble carboxymethylcellulose, water-soluble sodium carboxymethylcellulose [CAS 9004-32-4], water-soluble ethylmethyl cellulose, water-soluble hydroxyethylmethylcellulose [CAS 9032-42-2] ], water-soluble hydroxypropylmethylcellulose [CAS 9004-65-3], water-soluble hydroxyethylcellulose [CAS 9004-62-0], water-soluble ethylhydroxyethylcellulose, water-soluble sodium carboxy-methylhydroxyethylcellulose, water-soluble hydroxypropylcellulose [CAS 9004-64-2], water-soluble hydroxybutylcellulose [CAS 37208-08-5], water-soluble hydroxybutylmethylcellulose [CAS 9041-56-9] and sodium salt of water-soluble cellulose sulfate [CAS 9005-22-5]. Hydrosoluble hydroxypropylcellulose is preferred. The hydrosoluble hydroxypropyl cellulose is a known material and can be purchased commercially in several different weighted average molecular weights. The weight-average molecular weight of the water-soluble lydroxypropylcellulose used in the present invention can vary widely, but is usually in the range of 100,000 to 1,000,000. Frequently, the weighted average molecular weight is in the range of 100,000 to 500,000. It is preferred from 200,000 to 400,000. Two or more water-soluble hydroxyprocellulose having different weighted average molecular weights can be mixed to obtain a water-soluble hydroxypropylcellulose having a different weight average molecular weight. Similarly, there are many widely varying types of other water-soluble polymers that can be employed in the present invention. Examples include water-soluble poly (vinylpyridine), water-soluble poly (ethylene imine), water-soluble ethoxylated poly (ethylene imine), water-soluble poly (ethylene imine) epichlorohydrin, water-soluble polyacrylate, water-soluble sodium polyacrylate, water-soluble poly (acrylamide)., water-soluble car-boxi-modified poly (vinyl alcohol), water-soluble poly (2-acrylamido-2-methylpropanesulfonic acid), water-soluble poly (styrene sulfonate), water-soluble vinyl methyl ether / maleic acid copolymer, water-soluble styrene-non-copolymer -maleic anhydride, water-soluble ethylene-maleic anhydride copolymer, water-soluble acrylamide / acrylic acid copolymer, water-soluble poly (diethyltriaminthia-ad-acyl acid), water-soluble poly (methacrylate) (dimethyl-amino) -hydrochloride) water-soluble quaternized poly (imidazoline), water-soluble poly (N, N-dimethyl-3, 5-dimethylene piperidinium chloride), water soluble poly (vinyl pyridinium halide), water-soluble starch, oxidized starch 1? water-soluble, water-soluble casein, water-soluble gelatin, water-soluble sodium alginate, water-soluble carrageenan, water-soluble dextran, water-soluble gum arabic, water-soluble pectin, water-soluble albumin and water-soluble agar. Still other types of other water-soluble polymers that can be employed in the present invention include the water-soluble anionic polyacrylates and the water-soluble cationic polyacrylates. The hydrosoluble pol "ac" ilatc-an orb is well known per se. Normally, but not necessarily, they are copolymers of one or more (meth) acrylic esters and sufficient (meth) acrylic acid and / or (meth) acrylic acid salt to achieve sufficient carboxylate anions to render the polymer water-soluble. Similarly, the water-soluble cationic polyacrylates are well known per se, Normally, but not necessarily, they are copolymers of one or more (meth) acrylic esters and sufficient amino-functional ester of (meth) acrylic acid to obtain sufficient onium cations for make the acrylic polymer be. idrosoluble. The onium can be primary ammonium, ammonium. r. Undarium, ternary ammonium, quaternary ammonium, phosphonium or sulfonium- Secondary ammonium, tertiary ammonium or quaternary ammonium is preferred. Quaternary ammonium is especially preferred. Normally, the water-soluble cythionic polyacrylate is a primary, secondary, tertiary or quaternary ammonium salt, or is a quaternary ammonium hydroxide. Hydro-dispersible film-forming polymers, such as hydrodispersible poly (ethylene-co-acrylic acid) or water-dispersible cationic acrylic polymer, can be used. Polymers, oligomers and hydrophilic organic hydrophilic water-soluble or water-dispersible film-forming agents containing numerous ethylenically unsaturated groups can vary widely. In view of the enormous variations in structure, there are no marked boundaries or distinctions between polymers, oligomers and monomers. Frequently, the classification depends on whether it is seen as a repetitive unit, that is, a unit -mera. For example, trimethylolpropane, chain extended with oxy-1,2-ethanediyl groups and terminated in acryloyl groups, can be taken as a monomer if the trimethylolpropane moiety is considered as the central portion of a -mer unit, or can be taken as a polymer or oligomer, as the case may be, if oxy-1, 2-ethanodii is considered as a unit -mera. The number of ethylenically unsaturated groups contributed by each molecule can be zero, small or large, but, collectively, the molecules contain numerous ethylenically unsaturated groups. For the crosslinked polymer to be formed, at least a portion of the polymer, oligomer or monomer must contain at least two ethylenically unsaturated groups per molecule. In most cases, ethylenic unsaturation is provided by acryloyl groups, methacryloyl groups, allyl groups, vinyl groups, fumaroyl groups and maleoyl groups. Examples of such polymers, monomers and oligomers that may be used include polyacrylates, polymethacrylates, polyfumarates and water-soluble polymaleates of water-soluble poly (ethylene oxides) of low, medium or high molecular weight. Of particular importance are the water-soluble poly (ethylene oxide) diarylate [CAS 26570-48-9], the water-soluble poly (ethylene oxide) dimethacrylate [CAS 25852-47-5] and the poly (ethylene oxide) dimaleate ) water-soluble [CAS 36247-43-5]. Other examples are water-soluble poly (vinyl alcohols) in which the hydrogens of some of the hydroxyl groups have been replaced by acryloyl or methacryloyl groups. Still other examples include water-soluble or water-dispersible materials formed by chain extension of a central unit with oxy-1,2-ethanediyl groups and termination with acryloyl or methacryloyl groups. Examples of central groups that can be used include diols, aliphatic or aromatic triols and tetroles extended with oxy-1,2-ethanediyl, such as, for example, trimethylolpropane, glycerin, bisphenol A, propylene glycol and pentaerythritol. Hydrosoluble or water-dispersible organic polymers, oligomers and monomers containing an ethylenically unsaturated group per molecule may also be present. In most cases, the ethylenic unsaturation is by acryloyl groups, methacryloyl groups, allyl groups, vinyl groups, fumaroyl groups and maleoyl groups. Examples of such polymers, oligomers and monomers include the water-soluble mono-alkyl, monomethacrylate, monofumarate and monomaleonate of the water-soluble poly (ethylene oxide) and the extended aliphatic or aromatic diols, triols and tetraols with oxy-1,2-ethanediyl described in - previously. Of particular importance are water-soluble poly (ethylene oxide) monoacrylate [CAS 26403-58-7], water-soluble poly (ethylene oxide) monomethacrylate [CAS 25736-86-1] and poly (ethylene oxide monomaleate) ) water-soluble [CAS 37916-19-1]. Normally, the ratio of the number of ethylenically unsaturated groups per gram of the organic film-forming polymer present in the inorganic coating composition.

The number of ethylenically unsaturated groups per gram of the film-forming member present in the outer coating composition is less than 0.9: 1. Frequently, the ratio is less than 0.1: 1. Frequently, the ratio is less than 0.01: 1. In many cases, the reason is substantially zero. Typically, the organic film-forming polymer of the interior coating composition constitutes at least 1 percent by weight of the interior coating composition. In general, the organic film-forming polymer constitutes at least 3 percent by weight of the interior coating composition. In many cases, the organic film-forming polymer constitutes at least 5 percent of the inner coating composition. Often, the organic film-forming polymer constitutes from 1 to 40 weight percent of the interior coating composition. Frequently, the organic film-forming polymer constitutes from 2 to 30 weight percent of the interior coating composition. In many cases, the organic film-forming polymer constitutes from 3 to 20 weight percent of the interior coating composition. Similarly, the film-forming member of the outer coating composition constitutes at least 1 percent by weight of the outer coating composition. In general, the organic film-forming member constitutes at least 3 percent by weight of the outer coating composition. In many cases, the organic film-forming member constitutes at least 5 weight percent of the outer coating composition. Frequently, the organic film-forming member constitutes from 1 to 40 percent by weight of the outer coating composition. Frequently, the organic film-forming member constitutes from 2 to 30 percent by weight of the outer coating composition. In many cases, the organic film-forming member constitutes from 3 to 20 weight percent of the outer coating composition. When discrete non-film-forming particles having a number-average particle size of 1 to 500 nanometers are present in the dressing composition, they usually constitute at least 0.1 percent by weight of the coating composition. In general, discrete non-film-forming particles having a number average particle size of 1 to 500 nanometers constitute at least 1 percent by weight of the coating composition. In many cases, discrete non-film forming particles having a number average particle size of 1 to 500 nanometers constitute at least 2 weight percent of the coating composition. Frequently, discrete non-film forming particles having a number average particle size of 1 to 500 nanometers constitute from 0.1 to 30 percent by weight of the coating composition. Frequently, non-film-forming discrete particles having a number average particle size of 1 to 500 nanometers make up 1 to 25 weight percent of the coating composition. In many cases, discrete non-film forming particles having a number average particle size of 1 to 500 nanometers make up 2 to 20 weight percent of the coating composition. A material that may possibly be present in the coating composition is a mordant. For the purposes of the present description and claims, it is considered that a mordant is not part of the organic film-forming polymer. Mordants, also known as ink-fixing agents, are materials that interact, usually by reaction or absorption, with the binder, dye and / or pigment of the ink applied to the coated substrate. There are many mordants available that can be used. Suitable mordants include, but without limitation, poly (ethylene imines), ethoxylated poly (ethylene imines) and other poly (ethylene imine) derivatives. Examples include Lupasol ™ SC-ßlB (BASF Aktiengesellschaft) ink fixative, Lupasol ™ SC-62J (BASF Aktiengesellschaft) and Lupasol ™ SC-86X (BASF Aktiengesellschaft), Lupasol ™ PS (BASF Aktiengesellschaft), mordant. Lupasol ™ G-35 (BASF Aktiengesellschaft), and Lupasol ™ FG (BASF Aktiengesellschaft). When used, the amount of mordant present in the coating composition can vary considerably. In such cases, the weight ratio of the mordant to the organic film-forming polymer is in the range of 0.5: 100 to 30: 100. Frequently, the weight ratio is in the range of 0.5: 100 to 20: 100. Often, the weight ratio is in the range of 1: 100 to 10: 100. It is preferred from 2: 100 to 5: 100. These reasons are based on the dry solids of the mordant and the dry solids of the organic film-forming polymer. Another material that may possibly be present in the coating composition is a surfactant. For the purposes of the present description and the claims, it is considered that a surfactant is not part of the organic film-forming polymer. There are many available surfactants and combinations of surfactants that can be used. Examples of suitable surfactants include, but are not limited to, the surfactant Fluorad® FC-170-C (3M Company) and the surfactant Triton® X-405 (Union Carbide Corporation). When used, the amount of surfactant present in the coating composition can vary considerably. In such cases, the weight ratio of the surfactant to the hydrophilic organic film-forming polymer is usually in the range of 0.01: 100 to 10: 100. In many cases, the weight ratio is in the range of 0.1: 100 to 10: 100. Often, the weight ratio is in the range of 0.2: 100 to 5: 100. It is preferred from 0.5: 100 to 2: 100. These reasons are based on the dry solids of the surfactant and the dry solids of the hydrophilic organic film-forming polymer. There are many other conventional adjuvant materials that may optionally be present in the coating composition. These include "materials such as lubricants, waxes, plasticizers, antioxidants, organic solvents, lacquers and pigments." The list of such materials is by no means exhaustive, and these and other ingredients can be used in their usual amounts for their usual purposes, in to the extent that they do not seriously interfere with the good practice of the formulation of coating compositions.The coating compositions are normally prepared by simply mixing the various ingredients.The ingredients can be mixed in any order.While the mixture of liquid and solids is normally performed at room temperature, sometimes elevated temperatures are used.The maximum temperature that can be used depends on the thermal stability of the ingredients.The coatings are formed by application of coating compositions using any conventional technique known in the art. -riza Tilting, turning, curtain coating, immersion, rod coating, pallet coating, roller application, pressure by size, printing, brushing, dragging, slot die coating and extrusion. The exterior coating composition can be applied to the interior coating with or without significant removal of the first volatile aqueous liquid from the interior coating prior to application. The same coating composition can be applied once or multiple times. When the same coating composition is applied multiple times, the applied coating composition can be applied with or without significant prior removal of volatile aqueous liquid from the coating or precoats. After the application of a coating composition, the volatile aqueous liquid may be partially or totally removed from one or more of the coatings. After the final application of the final coating composition, the volatile aqueous liquid is partially or totally removed from one or more of the coatings. This can be achieved by any conventional drying technique. The thickness of the inner lining can vary widely, but, in most cases, the thickness of the inner lining is in the range of 1 to 30 μm. In many cases, the thickness of the inner lining is in the range of 5 to 20 μm. It is preferred from 8 to 18 μm. Similarly, the thickness of the outer coating may vary widely, but usually the thickness of the outer coating is in the range of 0.1 to 10 μm. Frequently, the thickness of the outer coating is in the range of 0.5 to 5 μm. 0.7 to 3 μm is preferred. The substrate can be any substrate, at least one surface of which is capable of carrying the coating discussed above. In most cases, the substrate is in the form of a single sheet or in the form of a roller, net, strip, film or sheet of material capable of being cut into sheets. It may be an uncoated material or it may be the exposed coating of a material that has been previously coated with one or more coatings. The substrate can be porous all the way through, it can be non-porous all the way through or it can have porous regions and non-porous regions. Examples of porous substrates include paper, cardboard, wood, cloth, non-woven fabric, felt, non-vitrified ceramic material, polymer membranes, porous foam and microporous foam. Examples of substrates that are substantially non-porous to their full extent include films or films of organic polymer, such as polyethylene terephthalate, polyethylene, polypropylene, cellulose acetate, polyvinyl chloride and copolymers such as saran The sheets or films can be metallized or non-metallized, as desired. Further examples include metal substrates, including, but not limited to, metal foils such as aluminum foil and co-bre leaf. Still another example is a porous or microporous foam consisting of a thermoplastic organic polymer, whose foam has been compressed to such an extent that the material of 2% The resulting formed is substantially non-porous. Still another example is glass. Base stocks that are normally porous, such as, for example, paper, cardboard, wood, cloth, non-woven fabric, felt, non-vitrified ceramic material, polymeric membranes, porous foam or microporous foam, can be coated or laminated to make a or more surfaces are substantially non-porous and thus obtain substrates having at least one substantially non-porous surface. The substrate may be substantially transparent, may be substantially opaque or may be of intermediate transparency. For some applications, such as upper slides printed by inkjet, the substratum must be transparent enough to be useful for that application. For other applications, such as inkjet printed paper, the transparency of the substrate is not as important. After the water absorbing inner lining and the intermediate outer lining have been formed on the surface of the substrate, they are exposed to actinic light, ionizing radiation or heat to provide the outer lining with numerous crosslinks derived from ethylenically unsaturated groups present in the polymer. hydrophilic organic applied coating composition. This procedure is known as "curing". Some, or substantially all, of the ethylenically unsaturated groups can be converted to crosslinks, as desired. The numbers of cross-links present in the outer coating must, in any case, be sufficient to increase the resistance to moisture stains of the print medium printed with ink jet in comparison with the same outer coating that has not been exposed to it. actinic light, ionizing radiation or heat according to this invention. When the outer intermediate coating is to be exposed to actinic light, a photoiniti, a photosensitizer or a mixture of photoiniti and photosensitizer is normally present. Normally, actinic light is ultraviolet light having a wavelength in the range of about 185 to about 400 nanometers. Photoinitis are compounds that absorb photons and thus obtain energy to form pairs of radicals, at least one of which is available to initiate polymerization by the addition of ethylenically unsaturated groups in a manner that is well known. Photosensitizers are compounds that are good absorbers of photons, but are themselves poor photoinitis. They absorb photons to produce excited molecules that then interact with a second compound to produce free radicals suitable for the initiation of addition polymerization. The second compound can be a monomer, a polymer or an added initi. Examples of photoinitis are benzoin, methyl benzoin ether, butyl benzoin ether, isobutyl benzoin ether, α, α-diethoxyacetophenone and α-chloroacetophenone. Examples of photosensitizers are benzyl, 1-naphthaldehyde, anthraquinone, benzophenone, 3-methoxybenzophenone, benzaldehyde and anthrone. The amount of photoiniti, photosensitizer or mixture of photoiniti and photosensitizer present in the outer coating composition and in the outer intermediate coating can vary widely. When any of these materials is present, the amount is usually in the range of 0.001 to 10 weight percent of the binder of the coating composition and the outer intermediate coating. More often, the amount is in the range of 0.002 to 8 weight percent of the binder. An amount in the range of 0.005 to 5 weight percent of the binder is preferred. When the outer intermediate coating is to be exposed to ionizing radiation, these materials are normally omitted from the outer coating composition and, therefore, of the outer intermediate coating, although its presence is permissible. Any suitable source emitting ultraviolet light, i.e., electromagnetic radiation having a wavelength in the range of about 180 to about 400 nanometers, can be used in the practice of this invention. Since said ultraviolet light has insufficient energy to produce ions in a medium composed of common elements, such as air or water, it is considered as non-ionizing radiation. Suitable sources of ultra-violet light are mercury arcs, carbon arcs, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, whirlpool plasma flow arc. and the ultraviolet light emitting diodes. Particularly preferred are ultraviolet light emitting lamps of the medium or high pressure mercury vapor type. Such lamps usually have quartz shells fused to withstand heat and to transmit ultraviolet radiation and are ordinarily in the form of long tubes having an electrode at both ends. The exposure times to actinic light and the intensity of the actinic light to which the polymerizable composition is exposed can vary greatly. Normally, exposure to actinic light is continued at least until many, and, in some cases, most, of the photoinitiator and / or photosensitizer molecules have been activated. The ionizing radiation employed in the invention is radiation having an energy at least sufficient to produce ions directly or indirectly in a medium composed of common elements, such as air or water, and includes radiation of ionizing particles and ionizing electromagnetic radiation. Ionizing particle radiation represents the emission of electrons or accelerated nuclear particles, such as protons, alpha particles, deutero-nes, beta particles, neutrons or their analogues. Charged particles can be accelerated using devices such as resonance chamber accelerators, DC potential gradient accelerators, betatrons, synchrotrons, cyclotrons, etc. Neutron radiation can be produced by bombarding a selected light metal, such as beryllium, with positively charged, high-energy particles. Radiation of ionizing particles can also be obtained through the use of an atomic battery, radioactive isotopes or other natural or synthetic radioactive materials. Ionizing electromagnetic radiation consists of high energy photons. Examples are X-rays, photonic radiation of electromagnetic braking and gamma rays. X-rays can be produced when a metal target, such as tungsten, copper or molybdenum, is bombarded with electrons of adequate energy. This energy is conferred to the electrons by accelerators, normal, but not necessarily, of the linear type. Ordinarily for this purpose, traveling wave linear accelerators, linear wave accelerators and linear accelerators with a DC potential gradient are used for this purpose. Photonic electromagnetic braking radiation, also known as continuous X-rays, is produced by the deceleration of electrons. The continuum extends from a short wave limit dependent on the maximum energy of the electrons indefinitely to the long wavelength end of the spectrum. Gamma rays can be obtained by means of a nuclear reactor, such as a cell, by the use of natural or synthetic radioactive materials, such as cobalt 60 or radio, which emit gamma rays, or by absorption of a neutron in the reaction ( n,?). Ionizing radiation, either particle radiation or electromagnetic radiation, ordinarily has an energy of at least about 10 electronic volts. While there is no upper limit for the ionizing radiation energy that can be used advantageously, the desired effects in the practice of this invention can be achieved without resorting to the use of ionizing radiation with energies greater than about 20,000,000 electronic volts. Accelerated electrons are the preferred ionizing radiation for the crosslinking coatings of the radiation curable coating co-deposition. The photonic radiation of electromagnetic braking generated by the deceleration of electrons is also present and probably contributes to the cross-linking. Several types of linear electronic accelerators are known, for example - the ARCO type traveling wave accelerator, model Mar I, which operates at 3 to 10 million electronic volts, supplied by High Voltage Engineering Corporation, Burlington, Massachusetts, or other types of accelerators, such as those described in US Pat. No. 2,763,609 and British Patent Description No. 762,953, which are satisfactory for the practice of this invention. Normally, electrons are accelerated to energies in the range of approximately 10,000 electronic volts to approximately 1,000,000 electronic volts. Typically, the energy is in the range of approximately 20,000 electronic volts to approximately 500,000 electronic volts. Preferably, the energy is in the range of approximately 25,000 electronic volts to approximately 200,000 electronic volts. The dose unit of ionizing radiation is the "rad", which is equal to 100 ergs of energy absorbed from the ionizing radiation per gram of material that is being irradiated. The dose is initially determined using an absolute method, such as calorimetry or ionization dosimetry. These absolute methods are quite sophisticated and, therefore, are not practical, in general, for routine determinations. Once a radiation field has been explored by an absolute dosimetry method, it is possible to calibrate secondary radiation indicators in that field using relative dosimetry techniques. A simple method of relative dosimetry is based on the whitening of blue zeal by ionizing radiation. The blue cellophane is exposed to a standard source for a known time and the light transmittance is measured with a wavelength of 655 nanometers with a spectrophotometer. The transmittance of the unexposed cellophane is also measured and the percentage change in transmittance due to exposure to ionizing radiation is calculated. Thanks to several readings and calculations of this type, a graph can be constructed that talks about the change in transmittance with the dose. A blue cellophane manufactured by E.l. du Pont de Nemours &; Company for this purpose. The calibrated blue cellophane can then be used to calibrate other sources of the same type of radiation and other types of blue cellophane that can be used in this routine work. Celcophane Avisco 195 CMS light blue manufactured by the American Viseóse Division of FMC Corporation has been calibrated and has been used for routine dose determinations. In practice, the calibrated blue cellophane is exposed to the ionizing radiation before, after or simultaneously to the coated substrate that is being irradiated. It is considered that the dose received by the coating is the same as that received by the blue cellophane. This assumes that the absorption of energy by the coating is the same as that of blue cellophane. Except for materials that contain fairly large proportions of atoms of very high atomic weight, the absorption of ionizing radiation is practically independent of the identity of the material. The assumption is, therefore, valid for the ordinary work of manufactured coatings where high degrees of accuracy of dose measurement are not necessary. As used throughout the specification and the claims, the dose is related to bleaching of calibrated blue cellophane film regardless of the identity of the coating composition being irradiated. Coatings of the radiation curable coating composition ordinarily receive a dose of ionizing radiation in the range of about 0.01 me-garad to about 20 megarads, although doses greater than 20 megarads can be used satisfactorily. The dose, however, should not be so large that the chemical or physical properties of the coating are severely altered. Typically, the dose is in the range of about 0.1 megarad to about 20 megarad. The preferred dose is in the range of about 1 megarad to about 10 megarads. The free-radical curing of ethylenically unsaturated groups of many, but not all, of the coatings containing such groups is significantly inhibited by oxygen when exposed to the coatings to actinic light or ionizing radiation. In such cases, the surface of the coating remains infracted. Often, inhibition by oxygen is so severe that even massive exposures to very large amounts of actinic light or ionizing radiation will not cure the surface to the desired extent. When the coating has a sufficient thickness and when exposed to the coating to actinic light or ionizing radiation, inhibition by oxygen may result in a surface layer of the coating having a significantly less degree of cure than the interior of the coating. When oxygen inhibition does occur, the effect can sometimes be reduced by the inclusion of materials that inhibit inhibition by oxygen. Inhibition by oxygen can always be reduced by significantly reducing the molecular oxygen concentration of the atmosphere in contact with the coating during exposure. The control of the oxygen inhibition can in some cases be used to vary the degree of curing so as to increase the stain resistance by humidity of the printing medium. The parameters that affect the inhibition by oxygen can often be used to vary the resistance to stains by moisture. These include the identities of the polymers, oligomers and monomers of the coating composition, the concentration of molecular oxygen in the atmosphere in which exposure to radiation occurs and the intensity of the actinic light or ionizing radiation. In the case of actinic light, the identities and amounts of actinic light absorbers can sometimes be used. See U.S. Patent No. 4,170,663, the disclosure of which is hereby incorporated by reference in its entirety, for a discussion of the general principles. When it is necessary to polymerize the ethylenically unsaturated groups of the outer intermediate coating by heating the external intermediate coating at high temperatures, a thermal initiator is normally present. The thermal initiators that can be used in the present invention can vary widely, but, in general, are thermally decomposable to produce pairs of radicals. One or both of the two radical pair members can be available to initiate the addition polymerization of the ethylenically unsaturated groups in a well known manner. Preferred thermal initiators are peroxy initiators. Examples of suitable peroxy initiators include esters of peroxydicarbonate, such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-isobutyl peroxydicarbonate, peroxydicarbonate di (2-ethylhexyl), diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate and iso-propyl-sec-butyl peroxydicarbonate; diacetyl peroxides, such as diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide and diisobutyryl peroxide, and peroxy esters, such as tertiary butyl perpivalate, tertiary butyl peroctoate and tertiary butyl perneodecanoate. Other examples of suitable peroxy initiators include monoperoxycarbonates, such as tert-butylperoxyisopropyl carbonate and tert-amylperoxyisopropyl carbonate. Only one initiator or a plurality of thermal initiators may be used, as desired. The amount of thermal initiator present in the outer coating composition and in the outer intermediate coating can vary widely. When the thermal initiator is present, the amount is usually in the range of 0.001% to 10% by weight of the binder of the coating composition and the outer intermediate coating. More often, the amount is in the range of 0.01 to 8 weight percent of the binder. An amount in the range of 0.1 to 5 weight percent of the binder is preferred. Normally, thermal polymerization is carried out at temperatures in the range of 28 ° C to 150 ° C. Often, the temperature is in the range of 35 ° C to 140 ° C. In many cases, the temperature is in the range of 50 ° C to 130 ° C. Exposure times at high temperatures can vary greatly. In general, heating is continued until most of the ethylenically unsaturated groups are polymerized. The coatings can be, collectively, substantially transparent, substantially opaque or of intermediate transparency. They may be substantially colorless, may be highly colored or may be of an intermediate degree of color. Preferably, the coatings are substantially transparent and substantially colorless. As used herein and in the claims, the coatings are collectively transparent if their luminous transmission in the visible region is at least 80 percent of the incident light. Frequently, the luminous transmission of the coating is at least 85 percent of the incident light. Preferably, the collective luminous transmission of the coatings is at least 90 percent. Also as used herein and in the claims, the coatings are collectively colorless if the light transmission is substantially the same for all wavelengths in the visible region, ie, 400 to 800 nanometers. The gloss of the water absorbing outer coating of the printing medium can vary widely. Although lower gloss is acceptable for many purposes, it is preferred that the gloss be at least 20. As used herein, the gloss is determined according to the TAPPI Standard T653 pm-90. An impression may optionally be made on the outer coating by applying droplets of liquid ink to the outer coating. This is most often done by inkjet printing. The droplets of liquid ink can be applied to the outer coating before removing the second volatile aqueous liquid from the outer coating or after having removed the second volatile aqueous liquid from the outer coating. The droplets of liquid ink can be applied to the outer coating before the substrate, the inner coating and the outer coating are exposed to actinic light, ionizing radiation or heat to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups. present in the applied outer coating composition. Alternatively, the droplets of liquid ink can be applied to the outer coating after the substrate, the inner coating and the outer coating have been exposed to actinic light, ionizing radiation or heat to provide the outer coating with numerous crosslinks derived from the ethylenically active groups. unsaturated in the applied outer coating composition. The invention is further described together with the following examples, which are to be considered as illustrative rather than limiting and in which all parts are parts by weight and all percentages are percentages by weight, unless otherwise indicated. EXAMPLE 1 The charts shown in Table 1 were used in the preparation of an aqueous dispersion of cationic acrylic polymer. TABLE 1 Ingredients Weight, kilograms Load 1 Methyl ethyl ketone 55.93 Loading 2 Methyl ethyl ketone 28, 67 Initiator 1 10.16 Charge 3 n-Butyl acrylate 30.44 Methyl methacrylate 87.32 2- (tert-Butylamino) ethyl methacrylate 40, 64 [CAS 3775-90-4] Styrene 44, 68 Charge 4 Methyl ethyl ketone 2.27 Charge 5 Methyl ethyl ketone 2.27 Charge 6 Glacial acetic acid 9.89 Methyl ethyl ketone 2.27 Charge 7 Deionized water 579.1 Charge 8 Deionized water 11.1 1 VAZO 67, 2, 2 '-azobis initiator ( 2-methylbuta-nitrile), El du Pont de Nemours and Company, Wilmington, Delaware. Charge 1 was heated in a reactor with stirring at reflux temperature (80 ° C). The addition of Charge 2 from a catalyst tank to the reactor was then initiated. The addition of Load 2 was made over a period of 305 minutes. After 5 minutes of the addition of Charge 2, the addition of Charge 3 of a monomer tank was initiated. The addition of Charge 3 was made over a period of 240 minutes. When the addition of Charge 3 was completed, charge 4 was added to the monomer tank as a wash and the wash liquid was then added from the monomer tank to the reactor over a period of 10 minutes. After the addition of Charge 2 was completed, the charge 5 was added to the catalyst tank as a wash and then the washing liquid from the catalyst tank was added to the reactor over a period of 10 minutes. The reaction mixture was then stirred at reflux for three hours, while the temperature of the reaction mixture was in the range of 83 ° C to 86 ° C. At the end of the three hour period, the reaction mixture was cooled to temperatures in the range of 48 ° C to 52 ° C. Charge 6 was added over a period of 10 minutes and the reaction mixture was then stirred for 15 minutes. Charge 7 was added to a clearing tank equipped for distillation and heated to temperatures in the range of 48 ° C to 52 ° C. The reaction mixture was dropped from the reactor to the clearing tank as quickly as possible. Charge 8 was added to the reactor as a wash and the wash liquid was also allowed to fall into the clearing tank. The contents of the clearing tank were agitated for 30 minutes at temperatures in the range of 48 ° C to 52 ° C. Over a period of thirty minutes, the pressure was reduced to 71.3 kilopascals, absolute. The temperature was then increased and the liquid removed in vacuo until the solids content of the batch was about 30 weight percent. The resulting product, which was an aqueous dispersion of cationic acrylic polymer, was cooled to about 48 ° C, filtered and then discharged in drums. The fillers shown in Table 2 were used in the preparation of a first aqueous composition of quaternary cationic polymer.

TABLE 2 Ingredients Weight, kilograms Load 1 Deionized water 100.0 Aqueous isopropanol1 200.0 Initiator2 5.0 Load 2 Methyl methacrylate • 20.0 Styrene 20.0 n-Butyl acrylate 15.0 Quaternary aqueous monomer3"56.3 1 70% Isopropanol, 30% water, by weight 2 VAZO® 67, 2, 2'-azobis (2-methylbutanonitrile) initiator, Du Pont de Nemours and Company, Wilmington, Delaware ^ [2- (methacryloyloxy) methylsulfate ) ethyl] trimethylammonium 80%, 20% water, by weight Charge 1 was heated to 75 ° C. Charge 2 was introduced in Charge 1 at 75 ° C over a period of 3 hours. then stirred the reaction mixture for 5 hours at 80 ° C. The isopropanol was removed by extracting in a Rotavapor at 60 ° C. Water was added to obtain a first aqueous composition of quaternary cationic polymer having a solids content of 25.5. % by weight Pseudoboehmite powder Disperal P2 (Condea, Germany) (140 grams) was gradually added to a solution of Dilute broth of nitric acid (860 grams, 0.25%) with agitation. The mixture was stirred until a translucent dispersion of pseudoboehmite was obtained. To a plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (200 grams) was added., 6%). While the solution was being stirred, a portion of the above aqueous dispersion of cationic acrylic polymer (24.0 grams, 29.4%), a portion of the above aqueous composition of cationic quaternary polymer (40.0) was added. grams, 25.5%) and Cymel 1172 urea / glyoxal adduct (Cytec Industries, Inc., West Pat-terson, New Jersey) (3.3 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. The product was an interior coating composition. To another plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (280 grams, 6%) was added. While the solution was being stirred, a portion of the above pseudoboehmite dispersion (72.0 grams, 14%), ChemCor 540C cationic polyethylene emulsion (ChemCor Inc., Chester, New York) (11.7 grams, 25%), ethoxylated trimethylolpropane finished in triacrilate Sartomer SR415 (12.0 grams, 100%) and adduct of urea / glyoxal Cymel 1172 (3.3 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. At the end, Darocure 1173 hydroxymethylphenylpropanone photoinitiator (Ciba-Geigy Corp., Tarrytown, New York) (0.4 grams) was added and the aqueous dispersion was stirred for 10 minutes to produce an outer coating composition. A portion of the interior lining composition was made to fall on foil-based stock paper Glory Base (Felix Schoeller, Germany) using a Meyer Rod # 160. The wet coating was dried in an oven at 105 ° C for 3.5 minutes to form an inner coating on the substrate. The thickness of the inner coating was approximately 15 μm. A portion of the outer coating composition was deposited on the inner coating by rod coating using a Meyer # 14 Rod. The wet coating was dried in the oven at 105 ° C for 3.5 minutes to produce an outer coating. The thickness of the outer coating was in the range of 1 to 2 μm. The coated substrate was passed once, at a speed of 21.3 meters / min. , in an air atmosphere, under two mercury vapor arc lamps, which emit ultraviolet light. The lamps were placed 6 inches above the surface of the coated substrate by passing it under the lamps. The dose was 500 mJ / cm2. The product was a means of printing. EXAMPLE 2 A printing medium was prepared as described in Example 1, except for the fact that exposure to ultraviolet light was carried out under a nitrogen atmosphere, in which the oxygen content was maintained below 100 ppm. EXAMPLE 3 The fillers shown in Table 3 were used in the preparation of a second aqueous composition of quaternary cationic polymer. TABLE 3 Ingredients Weight, kilograms Load 1 Isopropanol 100.0 Load 2 Isopropanol 106.5 Primer1 18.2 Load 3 Isopropanol 205.7 Styrene 182.5 Aqueous quaternary monomer2 243.3 Load 4 Deionized water 790 initiator VAZO® 67, 2, 2'-azobis (2- methylbutanonitrile), The du Pont de Nemours and Company, Wilmington, Delaware. 2 [2- (methacryloyloxy) ethyl] trimethylammonium chloride, 20% water, by weight. Charge 1 was heated in a reactor with reflux stirring (77 ° C-80 ° C). At reflux, Charge 2 was added over a period of 3 hours. After adding Load 2, the addition of Load 3 was started. Load 3 was added over a period of 3 hours. Charge 4 was added to the catalyst tank and to the monomer tank as a wash and was used for further additions of deionized water. After completing the additions of Charge 2 and Charge 3, the reaction mixture was stirred at reflux for 4 hours. The reactor was then adjusted for total distillation. Approximately 300 grams of deionized water was added to the reactor, the jacket temperature was reduced and vacuum was applied slowly. The vacuum distillation was started. After collecting 491 grams of distillates and adding an additional 490 grams of deionized water, vacuum distillation was continued. After removing most of the isopropanol, the percentage of solids was determined and the product was adjusted to 29.5 percent solids (determined by the weight difference of a sample before and after heating to 110 ° C during one hour) . The product, which was a second quaternary cationic polymer aqueous composition, was filtered through a 5 micron glass fiber filter. To a plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (200 grams, 6%) was added. While the solution was being stirred, a portion of the above aqueous dispersion of cationic acrylic polymer (48.5 grams, 29.4%), a portion of the second aqueous composition of quaternary cationic polymer (7.6 grams, 29.5%), a portion of the former dispersion of pseudoboehmite (50 grams, 14%) and adduct of urea / glyoxal Cymel 1172 (5.3 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. The product was an interior coating composition. To another plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (200 grams, 6%) was added. While the solution was being stirred, a portion of the above alumina dispersion was added. (71.5 grams, 14%), a portion of the above aqueous cationic acrylic polymer dispersion (48.5 grams, 29.4%), ChemCor 540C cationic polyethylene emulsion (16.0 grams, 25%), trimethylolpropane ethoxylated finished in tria-crilato Sartomer SR415 (12.0 grams, 100%), adduct of urea / glyoxal Cymel 1172 (3.3 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. At the end, hydroxymethylphenylpropanone photoinitiator Darocure 1173 (0.4 grams) was added and the solution was stirred for 10 minutes to produce an outer coating composition. A portion of the interior backing composition was lowered onto a Glory Base paper using a Meyer Rod # 160. The wet coating was dried in an oven at 105 ° C for 3.5 minutes to form an inner coating on the substrate. The thickness of the inner coating was approximately 15 μm. A portion of the outer coating composition was lowered onto the inner liner using a # 14 Meyer Rod. The wet coating was dried in the oven at 105 ° C for 3.5 minutes to produce an outer coating. The thickness of the outer coating was in the range of 1 to 2 μm. The coated substrate was passed once, at a speed of 21.3 meters / min., In an air atmosphere, under two mercury vapor arc lamps, which emitted ultra-violet light. The lamps were placed 6 inches above the surface of the coated substrate by passing it under the lamps. The dose was 500 mJ / cm2. The product was a means of printing. EXAMPLE 4 To a plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (280 grams, 6%) was added. While the solution was being stirred, a portion of the above alumina dispersion (72.0 grams, 14%), ChemCor 540C cationic polyethylene emulsion (11.7 grams, 25%), ethoxylated trimethylolpropane finished in Sartomer triacrylate was added. SR415 (12.0 grams, 100%) and adduct of urea / glyoxal Cymel 1172 (3.3 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. The resulting product was an outer coating composition. A portion of the above coating composition of Example 1 was lowered onto Glory Base paper using a Meyer Rod # 160. The wet coating was dried in an oven at 105 ° C for 3.5 minutes to form an inner coating on the substrate. The thickness of the inner re-dress was approximately 15 μm. A portion of the outer coating composition of this Example 4 was lowered onto the inner liner using a Meyer Rod # 14. The wet coating was dried in the oven at 105 ° C for 3.5 minutes to produce an outer coating. The thickness of the outer coating was in the range of 1 to 2 μm. The coated substrate was passed once, at a speed of 4.18 meters / min., In an air atmosphere, through an electron beam processing system, 300 KeV-15mA, self-protected unit, manufactured by High Voltage Engineering, Inc. Operating conditions were 210 KeV and 5 mA. A dosimeter was used to measure radiation exposure. The dose received by the coated substrate was 5 Megarads. The resulting product was an im-press medium. EXAMPLE 5 To a plastic container, an aqueous solution of polyethylene oxide having a weight average molecular weight in the range of 300,000 to 450,000 (200 grams, 6%) was added. While the solution was being stirred, a portion of the above alumina dispersion was added. (60 grams, 14%), a portion of the above aqueous dispersion of cationic acrylic polymer (28.0 grams, 29.4%), a portion of the first aqueous composition of quaternary cationic polymer (25.4 grams, 25, 5%), ChemCor 540C cationic polyethylene emulsion (16, 0 grams, 25%), ethoxylated trimethylolpropane finished in triacrilate Sartomer SR415 (10.0 grams, 100%) and adduct of urea / glyoxal Cymel 1172 (3.6 grams, 50%). After each addition, the mixture was stirred until a homogeneous aqueous dispersion was obtained. The resulting product was an outer coating composition. A portion of the above coating composition of Example 3 was lowered onto Glory Base paper using a Meyer Rod # 160. The wet coating was dried in an oven at 105 ° C for 3.5 minutes to form an interior coating on the substrate. The thickness of the inner lining was approximately 15 μm. A portion of the outer coating composition of this Example 5 was lowered onto the inner coating by rod coating using a Meyer Rod # 14. The wet coating was dried in the oven at 105 ° C for 3.5 minutes to produce an outer coating. The thickness of the outer coating was in the range of 1 to 2 μm. The coated substrate was passed once, at a speed of 4.18 meters / min. , in an air atmosphere, through the electron beam processing system described in Example 4. The operating conditions were 210 KeV and 5 mA. A dosimeter was used to measure radiation exposure. The dose received by the coated substrate was 5 Megarads. The resulting product was a printing medium. Although the present invention has been described in relation to specific details of certain embodiments thereof, it is not intended to consider such details as limitations of the scope of the invention, except insofar as they are included in the appended claims.

Claims

Rei indications

. A method consisting of: (a) having a substrate having at least one surface; (b) forming an interior coating on the surface by applying to the surface an interior coating composition, consisting of: (1) a first volatile aqueous liquid and (2) a hydrophilic organic film-forming polymer solubilized in water or dispersed in water which is substantially free of ethylenically unsaturated groups or contains only a few ethylenically unsaturated groups; (c) forming an outer coating on the inner coating by applying to the inner coating an outer coating composition consisting of: (1) a second volatile aqueous liquid and (2) a film-forming member selected from the group consisting of: (A) a water-soluble hydrophilic organic film-forming polymer containing numerous ethylenically unsaturated groups; (B) a hydrophilic organic film-forming polymer dispersed in water containing numerous ethylenically unsaturated groups; (C) a hydrophilic organic film-forming oligomer solubilized in water containing numerous ethylenically unsaturated groups; (D) a water-dispersed hydrophilic organic film-forming oligomer containing numerous ethylenically unsaturated groups; (E) a hydrophilic organic film-forming monomer solubilized in water containing numerous ethylenically unsaturated groups; (F) a hydrophilic organic film-dispersing monomer dispersed in water containing numerous ethylenically unsaturated groups, and (G) a mixture of two or more of these; and (d) exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous crosslinks derived from the ethylenically unsaturated groups present in the applied outer coating composition; where; (e) the interior coating composition, the exterior coating composition or each of the interior coating composition and the outer coating composition further contain discrete particles which are not film-forming and which have a number average particle size. in the range of 1 to 500 nanometers; (f) a first volatile aqueous liquid is removed from the innerliner to produce an inner water-absorbing coating on the surface of the substrate, G) a second volatile aqueous liquid is removed from the outer coating to produce a water-absorbing outer coating on the surface of the water-absorbing inner liner.
2. The method of claim 1, wherein the interior coating composition contains discrete particles that are not film-forming and having a number average particle size in the range of 1 to 500 nanometers.
3. The method of claim 1, wherein the outer coating composition contains discrete particles that are not film-forming and having a number average particle size in the range of 1 to 500 nanometers.
4. The method of claim 1, wherein each of the interior coating composition and the outer coating composition contain discrete particles that are not film-forming and having a number average particle size in the range of 1 to 500 nanometers.
5. The process of claim 1, wherein the first volatile aqueous liquid is removed from the innerliner prior to the application of the outer coating composition to the innerliner.
6. The method of claim 1, wherein the first volatile aqueous liquid is removed from the innerliner after the application of the outer coating composition to the innerliner.
7. The method of claim 1, wherein the second volatile aqueous liquid is removed from the outer coating before exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups present in the film-forming member of the applied outer coating composition.
8. The method of claim 1, wherein the first volatile aqueous liquid is removed from the inner coating and the second volatile aqueous liquid is removed from the outer coating before exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups present in the film-forming member of the applied outer coating composition.
9. The method of claim 1, wherein the second volatile aqueous liquid is removed from the outer coating after exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups present in the film-forming member of the applied outer coating composition.
10. The method of claim 1, wherein the first volatile aqueous liquid is removed from the inner coating and the second volatile aqueous liquid is removed from the outer coating after exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat. to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups present in the film-forming member of the applied outer coating composition.
11. The method of claim 1, further including printing on the outer coating by applying droplets of liquid ink to the outer coating.
12. The method of claim 11, wherein the droplets of liquid ink are applied to the outer coating before removing the second volatile aqueous liquid from the outer coating.
13. The method of claim 11, wherein the droplets of liquid ink are applied to the outer coating after removing the second volatile aqueous liquid from the outer coating.
14. The method of claim 11, wherein the droplets of liquid ink are applied to the outer coating before exposing the substrate, the inner coating and the outer coating to actinic light, ion-izante radiation or heat to provide the outer coating with numerous cross-links derived of the ethylenically unsaturated groups present in the applied outer coating composition.
15. The method of claim 11, wherein the droplets of liquid ink are applied to the outer coating after exposing the substrate, the inner coating and the outer coating to actinic light, ionizing radiation or heat to provide the outer coating with numerous cross-links derived from the ethylenically unsaturated groups present in the applied outer coating composition.
16. the process of claim 1, wherein the discrete particles are discrete particles of alumina, silica or titania.
17. The process of claim 1, wherein the discrete particles are discrete particles of alumina monohydroxide.
18. The method of claim 1, wherein the discrete particles are discrete particles of pseudoboehmite.
19. The process of claim 1, wherein the discrete non-film forming particles constitute from 1 to 80 weight percent of the interior coating composition, the outer coating composition or each of the interior coating composition and the composition of exterior cladding.
20. The process of claim 1, wherein the hydrophilic organic film-forming polymer solubilized in water or dispersed in water of the inner coating composition consists of poly (ethylene oxide), poly (vinyl alcohol), poly (vinylpyrrolido-na), organic water-soluble cellulosic polymer or a mixture of two or more of these.
21. The process of claim 20, wherein the hydrophilic organic film-forming polymer of the inner coating composition consists of water-soluble poly (ethylene oxide) having a weight average molecular weight in the range of 100,000 to 3,000,000.
22. The process of claim 1, wherein the hydrophilic organic film-forming polymer solubilized in water or dispersed in water of the outer coating composition consists of poly (ethylene oxide), poly (vinyl alcohol), poly (vinylpyrrolido-na), organic water-soluble cellulosic polymer or a mixture of two or more of these.
23. The process of claim 22, wherein the hydrophilic organic film-forming polymer of the outer coating composition consists of water-soluble poly (ethylene oxide) having a weight average molecular weight in the range of 100,000 to 3,000,000.
24. The process of claim 1, wherein the ratio of the number of ethylenically unsaturated groups per gram of the film-forming organic polymer present in the inner coating composition to the number of ethylenically unsaturated groups per gram of the film-forming member present in the composition of exterior cladding is less than 0.9: 1.
25. The method of claim 1, wherein the film-forming organic polymer of the interior coating composition independently constitutes at least 1 percent by weight of the inner coating composition and the film-forming member of the outer coating composition constitutes the less 1 percent by weight of the outer coating composition.
26. The method of claim 1, wherein the non-film-forming discrete particles having a number average particle size of 1 to 500 nanometers constitute at least 0.1 percent by weight of the interior coating composition, the reverse composition. -Out exterior or each of the interior cladding composition and the exterior cladding composition.
27. The method of claim 1, wherein the substrate, the inner coating and the outer coating are exposed to ultraviolet light to provide the outer coating with numerous crosslinks derived from the ethylenically unsaturated groups present in the applied outer coating composition.
28. The product produced by the process of claim 1.
29. The product produced by the process of claim 2.
30. The product produced by the process of claim 3.
31. The product produced by the process of claim 4.
32. The product produced by the process of claim 11.
33. The product produced by the process of claim 16.
34. The product produced by the process of claim 17.
35. The product produced by the process of claim 18.
36. The product produced by the process of claim 19.
37. The product produced by the process of claim 20.
38. The product produced by the process of claim 21.
39. The product produced by the process of claim 22.
40. The product produced by the process of claim 23.
41. The product produced by the process of claim 24.
42. An article consisting of: (a) a substrate having at least one surface; (b) interior water-absorbing coating on the surface, wherein the water-absorbing inner coating consists of a hydrophilic organic polymer substantially free of cross-links derived from ethylenic unsaturation, or containing few crossings derived from ethylenic unsaturation, and (c) outer coating water absorbent on the water-absorbing inner lining, wherein the water-absorbing outer coating consists of a hydrophilic organic polymer containing numerous cross-links derived from ethylenic unsaturation; wherein: (d) the inner lining, the outer lining or each of the inner lining and the outer lining further contain discrete particles having a number average particle size in the range of 1 to 500 nanometers;
43. The article of claim 42, wherein the thickness of the inner coating is in the range of 1 to 30 μm and the thickness of the outer coating is in the range of 0.1 to 10 μm.