HK1062425B - Polymer processing of a substantially water resistant microporous substrate - Google Patents

Description

Polymer treatment of substantially water-resistant microporous substrates

Technical Field

The present invention relates to a multi-layer article comprising a substantially water-resistant, coated microporous substrate attached to a substantially non-porous material. Furthermore, the present invention relates to a method for producing a multilayer article.

Disclosure of Invention

Unless otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like used herein are to be understood as modified in all instances by the term "about. Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

The present invention relates to a multilayer article comprising a microporous substrate at least partially attached to a substantially nonporous material, the microporous substrate being at least partially coated with a substantially water resistant coating composition comprising a stable dispersion of:

(a) an aqueous polyurethane dispersion; and

(b) a cationic nitrogen-containing polymeric dye fixative material at least partially soluble in an aqueous medium.

Suitable microporous substrates for use in the present invention include microporous substrates known in the art such as cellulose-based papers. In addition, the following U.S. patents describe suitable microporous substrates for use in the present invention: 4,861,644, 4,892,779 and 5,196,262. In addition, a suitable microporous substrate for use in the present invention is described in U.S. patent application Ser. No.60/309,348 filed on 8/1/2001, which is pending in the patent office. The above patents and patent applications are incorporated herein by reference.

In embodiments, a microporous substrate having a top surface and a bottom comprises:

(a) a polyolefin;

(b) a particulate silica material; and

(c) pores, wherein pores constitute at least 35% by volume of the microporous substrate.

The polyolefins used in the microporous substrate of the present invention may include polyolefins known in the art such as polyethylene or polypropylene. In one non-limiting embodiment, the polyethylene is a substantially linear high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters/gram, and the polypropylene is a substantially linear high molecular weight polypropylene having an intrinsic viscosity of at least 5 deciliters/gram. As used herein and in the claims, "high molecular weight" means a weight average molecular weight of 20,000-2,000,000.

The intrinsic viscosity reported here and in the claims is determined by extrapolation to zero concentration reduced or inherent viscosity of several dilute polyolefin solutions, in which the solvent is distilled decalin, to which has been added 0.2% by weight of neopentanetetrayl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate (CAS registry No. 6683-19-8). The reduced or inherent viscosity of the polyolefin is determined from the relative viscosity obtained at 135 ℃ using an Ubbelohde No.1 viscometer according to the general procedure of ASTM D4020-81, except that several dilute solutions of different concentrations are employed. ASTM D4020-81 is incorporated herein by reference.

The particulate silica material used in the present invention may be selected from a wide variety of known materials. Suitable non-limiting examples include silica, mica, montmorillonite, kaolin, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, aluminum silicate, sodium aluminum silicate, polyaluminum silicate, alumina silica gel, and glass particles. Silica and clay are commonly used. In one non-limiting embodiment, precipitated silica, silica gel, or calcined silica is used. In another non-limiting embodiment, precipitated silica is used.

In general, silica can be prepared by combining an aqueous solution of a soluble metal silicate with an acid. The soluble metal silicate is typically an alkali metal silicate such as sodium or potassium silicate. The acid may be selected from inorganic acids, organic acids, and carbon dioxide. The silicate/acid slurry may then be aged. An acid or base is added to the silicate/acid slurry. The silica particles obtained are separated from the liquid part of the mixture. The separated silica is washed with water, the wet silica product is dried, and the dried silica is then separated from the residue of the other reaction products using conventional washing, drying and separation methods.

The silica produced by the above process may be a particulate material in the form of aggregates. These aggregates consist of substantially solid, substantially spherical particles known in the art as primary particles or elementary particles. In embodiments, the primary or primary particles may have a particle size of less than 0.1 micron as measured by a laser analyzer such as a Beckman Coulter LS 230. Methods for characterizing primary particles have been described in prior art references (e.g., "chemistry of silica" Ralph k. ile, 1979John Wiley & Sons, new york, chapter 5). It is known in the art that primary particles or elementary particles having a particle size of less than 0.1 micron exhibit a tendency to cluster together and form covalent siloxane bonds between the particles in addition to the siloxane bonds in the primary particles. These primary or elementary particles are assembled and clustered together to form an enhanced covalently bonded structure called an aggregate. In the silica used in the present invention, the aggregates have a particle size of 0.1 to 1 micron as measured by the Beckman Coulter LS230 described above. The aggregates aggregate and group together to form a loose agglomerate structure containing open pores.

In the present invention, at least 90 weight percent of the silica particles used to prepare the microporous substrate have a particle size in the range of 5 to 40 microns. Particle size was measured according to ASTM C690-80 using a model TaII Coulter Multisizer particle size analyzer (Coulter Electronics, Inc.), but modified by stirring the filler for 10 minutes in an isoton ii electrolyte solution (cutin Matheson Scientific, Inc.) using a four-bladed, 4.445 cm diameter propeller stirrer. In one non-limiting embodiment, at least 90 weight percent of the silica particles have a particle size in the range of from 10 to 30 microns.

U.S. patent nos. 2,940,830 and 4,681,750, and U.S. patent application serial No. 09/882,549 (filed on 14/7/2001 and pending), describe suitable precipitated silicas for use in the present invention and methods for their preparation.

In one non-limiting embodiment, the silica particles are finely divided. As used herein and in the claims, "finely divided" means a maximum retention of 0.01 wt% on a 40 mesh screen.

In one non-limiting embodiment, the silica particles are substantially insoluble. "substantially insoluble" as used herein and in the claims means water solubility as follows: it may be in the range of 70ppm to greater than 150ppm in water at a temperature of 25 ℃. It is believed that the change in solubility is due to differences in particle size, the state of internal hydration and the presence of trace impurities absorbed in the silica or on its surface. The solubility of silica is also dependent on the pH of the water. The solubility of silica can increase as the pH increases from neutral (i.e., pH of 7) to alkaline (i.e., pH greater than 9). (see "chemistry of silica", R.K. Iler, Wiley-Interscience, NY (1979), pages 40-58).

In one non-limiting embodiment, the silica particles used in the present invention are coated prior to incorporation into the microporous substrate. U.S. patent application nos. 09/636,711, 09/636,312, 09/636,310, 09/636,308, 09/636,311, and 10/041,114, which are incorporated herein by reference, disclose suitable coating compositions and methods for coating silica particles that can be used in the present invention. The coating may be applied by methods known in the art. The choice of method for coating the silica particles is not critical. For example, the coating ingredients may be added to an aqueous slurry of a pre-washed silica filter cake with sufficient agitation to allow thorough mixing of the ingredients, followed by drying using conventional techniques known in the art.

The particulate silica material comprises 50 to 90 wt% of the microporous substrate. In one non-limiting embodiment, the particulate silica material comprises 50 to 85 wt%, or 60 to 80 wt% of the microporous substrate.

The microporous substrate used in the present invention contains pores such that the pores constitute at least 35% by volume of the microporous substrate. The term "pore" as used herein and in the claims means a tiny opening through which a substance passes. In many cases, the pores constitute at least 60% of the volume of the microporous substrate. Typically, the pores constitute 35% to 95% of the volume of the microporous substrate. In one non-limiting embodiment, the pores constitute from 60% to 75% by volume.

In one non-limiting embodiment, the substrate is highly porous. The term "highly porous" refers to substrates having a porosity of no greater than 20,000, or no greater than 10,000, and in many cases no greater than 7,500 seconds per 100cc of air. The porosity is typically at least 50 seconds per 100cc of air. These porosity values were measured according to the method described in ASTM D726, with the following differences relative to ASTM section 8. In the present invention, sheet samples are tested without conditioning according to ASTM D685, and for a total of six (6) measurements of a given sample type (three measurements per two surfaces), only three (3) specimens of a given sample type are tested, instead of a minimum of ten specimens for a given sample as described in ASTM D726. The lower the number in seconds/cc of air, the more substrate pores.

Highly porous substrates can be produced by various methods known in the art, such as heat treating the substrate, orienting, compositionally increasing the silica content, microporosizing the membrane, or etching. Examples of highly porous substrates include heat treated microporous materials such as Teslin TS-1000, available from PPG Industries, Inc., Pittsburgh, Pa.

In addition to particulate silica materials, non-particulate silica materials that are substantially insoluble in water can also be used for the microporous substrate. Examples of such optional non-silica particles include particles of titanium oxide, iron oxide, copper oxide, zinc oxide, antimony oxide, zirconium oxide, magnesium oxide, aluminum oxide, molybdenum disulfide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate, magnesium hydroxide, and finely divided particles of substantially water-insoluble flame retardants such as particles of ethylene bis (tetrabromophthalimide), octabromodiphenyl ether, decabromodiphenyl ether, and ethylene bis-dibromonorbornane dicarboximide.

The microporous substrate used in the present invention may be coated with a substantially water-resistant coating composition. In one non-limiting embodiment, at least one side of the microporous substrate is coated with a substantially water-resistant composition. Examples of suitable coating compositions for use in the present invention include aqueous polyurethane dispersions, and stable dispersions of cationic nitrogen-containing polymeric dye fixative materials that are at least partially soluble in aqueous media. Suitable aqueous polyurethane dispersions include known water dispersible nonionic polyurethanes, anionic polyurethanes, cationic polyurethanes, and mixtures thereof. Polyurethane dispersions and their preparation are known, for example, Szycher ("Szycher's book of Michael Szycher," CRC Press, new york, NY, 1999, part 14) describes the preparation of various aqueous polyurethane dispersions.

The addition of an aqueous solution of a cationic nitrogen-containing polymer to an aqueous anionic polyurethane dispersion results in a stable dispersion which is useful as a coating composition for microporous substrates. However, reversing the order of addition allows the addition of the anionic polyurethane dispersion to the aqueous solution of the cationic nitrogen-containing polymer, which, if not stirred sufficiently, can result in the formation and precipitation of the poly salt from the aqueous solution.

In one non-limiting embodiment, the aqueous dispersion of anionic polyurethane resin for use in the present invention comprises particles of anionic polyurethane polymer dispersed in an aqueous medium. The polyurethane polymer contains at least one pendant acid group which can be neutralized in the presence of a base to form an anionic group which stabilizes the dispersion.

The anionic polyurethanes useful in the present invention can be prepared by methods known in the art. For example, the reaction of (i) a polyisocyanate, (ii) a polyol, (iii) a compound containing acid groups, and optionally (iv) a chain extending compound such as a polyamine or hydrazine, produces a suitable anionic polyurethane. As used herein and in the claims, "polyisocyanate" refers to a compound having more than 1 isocyanate group. Suitable polyisocyanates for use in the present invention include diisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; tri-or polyfunctional isocyanates which may be the reaction products of diisocyanates with polyols such as trimethylolpropane, glycerol and pentaerythritol. Suitable polyisocyanates for use in the present invention are commercially available from Bayer Corporation under the Desmodur trade name.

The term "polyol" as used herein and in the claims means a compound containing more than one hydroxyl group. Non-limiting examples of suitable polyols are simple polyols such as those used to prepare polyisocyanates, polyester polyols and polyether polyols.

The anionic polyurethanes used in the present invention may include acid groups such as carboxylic or sulfonic acid groups and both groups, which may be reacted with a polyisocyanate or a polyol. Non-limiting examples of groups that can react with a polyol are isocyanate groups. Non-limiting examples of groups that can react with the polyisocyanate include hydroxyl and amine groups. An example of a compound containing two hydroxyl and acid groups is dimethylolpropionic acid. Examples of polyamines include ethylenediamine, isophoronediamine or diethylenetriamine.

In one non-limiting embodiment, the anionic polyurethane dispersion used in the present invention can be dispersed using acidic groups on the ionized polymer and a base that stabilizes the dispersion. The base may comprise any known inorganic base, ammonia or amine.

The reaction of i) a polyacyanate, (ii) a compound containing an acid group, and (iii) a polyol in the presence of an organic solvent can be carried out to form an isocyanate-terminated prepolymer. Suitable organic solvents include n-methylpyrrolidone, tetrahydrofuran or glycol ethers. The isocyanate-terminated prepolymer may be dispersed in water in the presence of a base and then chain extended by the addition of a polyamine. In one non-limiting embodiment, the prepolymer is chain extended in an organic solvent solution and then the polyurethane polymer is dispersed in water in the presence of a base.

Non-limiting examples of suitable anionic polyurethanes for use in the present invention include anionic polyurethanes based on: aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, and/or aliphatic polycaprolactam polyurethanes. The anionic polyurethane dispersion used in the present invention is available under the trade name WitcoBond from Crompton corporation^And (4) obtaining the product.

The aqueous anionic polyurethane dispersion of the coating composition comprises at most 70 wt.%, or at most 65 wt.%, or at most 60 wt.%, or at most 50 wt.% of an anionic polyurethane. The aqueous anionic polyurethane dispersion comprises at least 1 wt.%, or at least 5 wt.%, or at least 10 wt.%, or at least 20 wt.% of anionic polyurethane. The amount of anionic polyurethane in the aqueous anionic polyurethane dispersion is not critical. Generally, the amount should not be so high as to cause instability of the dispersion by itself or in admixture with the nitrogen-containing polymer, or so low that the coating composition does not provide sufficient water and rub resistance or that the dispersion by itself becomes unstable. The anionic polyurethane may be present in the aqueous anionic polyurethane dispersion in any range of values, including those described above.

Various known water-dispersible cationic polyurethanes can be used as the cationic polyurethane dispersion in embodiments of the present invention. Suitable non-limiting examples of cationic polyurethanes are available from Crompton corporation under the trade name WitcoBond, for example, the WitcoBond W-213 and W-215 formulations.

The cationic polyurethanes can be prepared by methods known in the art. Us patent 3,470,310 discloses the preparation of aqueous polyurethane dispersions, the polyurethane comprising salt-type groups linked to the polyurethane. U.S. patent 3,873,484 discloses aqueous dispersions of polyurethanes prepared from quaternized polyurethane prepolymers prepared by reacting: alkoxylated diols, N-alkyldialkanolamines, organic diisocyanates and quaternization with dialkyl sulfate quaternizing agents. U.S. patent 6,221,954 teaches a process for preparing polyurethane prepolymers wherein a tertiary N-monoalkanol amine is reacted with an alkylene oxide in the presence of a strong acid to form a polyol salt, the polyol salt is further reacted with an excess of an organic polyisocyanate and chain extended with an active hydrogen containing compound. These references are incorporated herein by reference.

In one non-limiting embodiment, the aqueous cationic polyurethane dispersion used in the present invention comprises at most 70 wt.%, or at most 65 wt.%, or at most 60 wt.%, or at most 50 wt.% cationic polyurethane. In further non-limiting embodiments, the aqueous cationic polyurethane dispersion comprises at least 1 wt.%, or at least 5 wt.%, or at least 10 wt.%, or at least 20 wt.% cationic polyurethane. The amount of cationic polyurethane in the aqueous cationic polyurethane dispersion is not critical. Generally, the amount should not be so high as to cause instability of the dispersion by itself or in admixture with the nitrogen-containing polymer, or so low that the coating composition does not provide sufficient water and rub resistance or that the dispersion by itself becomes unstable. The cationic polyurethane can be present in the aqueous cationic polyurethane dispersion in any range of values, including those described above.

Any known water-dispersible nonionic polyurethane can be used as the nonionic polyurethane dispersion for use in the present invention. Non-limiting examples of suitable cationic polyurethanes are available from Crompton corporation under the trade name WitcoBond, for example, the WitcoBond W-230 formulation.

The nonionic polyurethanes can be prepared by methods known in the art. For example, Szycher (i.e., "Szycher's Book of Polyurethanes," CRC Press, New York, NY, 1999, pages 14-10 to 14-15 of Michael Szycher) describes the preparation of aqueous polyurethane dispersions, the Polyurethanes containing hydrophilic polyether-type groups that are branched from or at the ends of the main polyurethane chains. Polyethylene oxide units (molecular weight (MW) of 200-. Nonionic polyurethanes can be prepared using diols or diisocyanate comonomers with pendant polyethylene oxide chains.

In further non-limiting embodiments of the present invention, the aqueous nonionic polyurethane dispersion comprises at most 70 wt.%, or at most 65 wt.%, or at most 60 wt.%, or at most 50 wt.% nonionic polyurethane. The aqueous nonionic polyurethane dispersion comprises at least 1 wt.%, or at least 5 wt.%, or at least 10 wt.%, or at least 20 wt.% nonionic polyurethane. The amount of nonionic polyurethane in the aqueous nonionic polyurethane dispersion is not critical. Generally, the amount should not be so high as to cause instability of the dispersion by itself or in admixture with the nitrogen-containing polymer, or so low that the coating composition does not provide sufficient water and rub resistance or that the dispersion by itself becomes unstable. The nonionic polyurethane can be present in the aqueous nonionic polyurethane dispersion in any range of values, including those described above.

In non-limiting embodiments of the present invention, the cationic nitrogen-containing polymeric dye fixative material, which is at least partially soluble in an aqueous medium, has a pH of less than 7, or less than 6, or less than 5. A pH in this range allows at least a portion of the nitrogen atoms to carry at least a portion of the cationic charge. The coating composition obtained has a pH of less than 7, or less than 6, or less than 5.

Dye fixatives are generally used to at least partially fix dyes to a substrate to prevent the dyes from bleeding or migrating out of the substrate when the substrate is contacted with water.

Various known cationic nitrogen-containing polymers within the above-described pH ranges of the coating composition may be used in the coating composition of the present invention as dye fixatives. Non-limiting examples of suitable cationic nitrogen-containing polymers include cationic polymers comprising one or more monomer residues derived from one or more of the following nitrogen-containing monomers:

and

wherein R is¹Independently for each occurrence in each structure represents H or C₁-C₃An aliphatic group; r²Independently for each structure represents a group selected from C₂-C₂₀Divalent linking groups of aliphatic hydrocarbons, polyethylene glycol, and polypropylene glycol; r³H, C are represented independently for each case in each structure₁-C₂₂Aliphatic hydrocarbons or residues from the reaction of nitrogen with epichlorohydrin; z is selected from-O-or-NR⁴-, wherein R⁴Is H or CH₃(ii) a And X is halide or methylsulfate.

Non-limiting examples of nitrogen-containing monomers useful in preparing the polymeric dye fixative material of the present invention comprising the corresponding monomer residues or resulting monomer residues include dimethylaminoethyl (meth) acrylate, (meth) acryloxyethyltrimethylammonium halide, (meth) acryloxyethyltrimethylammonium methyl sulfate, (meth) aminopropyl (meth) acrylamide, (meth) acrylamidopropyltrimethylammonium halide, aminoalkyl (meth) acrylamides where the amine is reacted with epichlorohydrin, (meth) acrylamidopropyltrimethylammonium methyl sulfate, diallylamine, methyldiallylamine, and diallyldimethylammonium halides.

In additional non-limiting embodiments, additional monomers can also be used to prepare cationic nitrogen-containing polymers comprising residues of the corresponding monomers. Additional monomer residues may be obtained from any polymerizable ethylenically unsaturated monomer that, when copolymerized with the nitrogen-containing monomer, is suitable to provide a resulting polymer that is at least partially soluble in water. As used herein and in the claims, "partially soluble" means that when ten (10) grams of polymer is added to one (1) liter of water and mixed thoroughly for 24 hours, at least 0.1 grams of polymer is dissolved in deionized water.

Non-limiting examples of monomers that can be copolymerized with the nitrogen-containing monomer include (meth) acrylamide, n-alkyl (meth) acrylamide, (meth) acrylic acid, alkyl (meth) acrylates, glycol (meth) acrylates, polyethylene glycol (meth) acrylates, hydroxyalkyl (meth) acrylates, itaconic acid, alkyl itaconates, maleic acid, mono-and dialkyl maleates, maleic anhydride, maleimide, aconitic acid, alkyl aconitates, allyl alcohol, and allyl alcohol alkyl ethers.

In one non-limiting embodiment, the cationic nitrogen-containing polymer is a homopolymer of a nitrogen-containing monomer, or a copolymer of one or more nitrogen-containing monomers. In another non-limiting embodiment, the nitrogen-containing polymer is a copolymer of one or more polymerizable ethylenically unsaturated monomers and one or more nitrogen-containing monomers. In further non-limiting embodiments, when the nitrogen-containing polymer includes any of the above additional polymerizable ethylenically unsaturated comonomers, the nitrogen-containing polymer can include no greater than 70 mol%, or no greater than 50 mol%, or no greater than 25 mol%, or no greater than 10 mol% of the nitrogen-containing monomer. The amount of nitrogen-containing monomer may depend on the particular polyurethane used in the coating composition of the present invention. When the amount of nitrogen-containing monomer used in the nitrogen-containing polymer is too high, an unstable mixture of the nitrogen-containing polymer and the polyurethane dispersion may result.

In further non-limiting embodiments, when the nitrogen-containing polymer includes any of the above additional polymerizable ethylenically unsaturated comonomers, the nitrogen-containing polymer can include at least 0.1 mol%, or at least 1.0 mol%, or at least 2.5 mol%, or at least 5.0 mol% of the nitrogen-containing monomer. When the amount of the nitrogen-containing monomer in the nitrogen-containing polymer is too low (i.e., less than 0.1 mol%), the nitrogen-containing polymer may not provide adequate dye-fixing agent properties and the recorded ink image on the coated substrate may lack water and rubbing fastness properties.

The nitrogen-containing monomer may be present in the nitrogen-containing polymer in any range of values, including those described above. In addition the polymerizable ethylenically unsaturated monomers are present in an amount such that the total percentage is 100 mol%.

In further non-limiting embodiments of the present invention, the aqueous solution of cationic nitrogen-containing polymeric dye fixative agent may include at least 5 wt%, or at least 10 wt%, or at least 15 wt% of a nitrogen-containing polymer; and no greater than 50 wt%, or no greater than 45 wt%, or no greater than 40 wt% of a nitrogen-containing polymer. When the concentration of the nitrogen-containing polymer is too low, it is not economical for commercial use and may be too dilute to provide an optimal ratio to the polyurethane. When the concentration is too high, the solution may be too viscous to be easily handled in a commercial environment. An example of a cationic nitrogen-containing polymer for use in the present invention is a solution of a polyamidoamine reacted with epichlorohydrin, available under the trade name CinFIx from Stockhausen GmbH & Co.

The microporous substrate coating composition for use in the present invention comprises a mixture of an aqueous solution of a cationic nitrogen-containing polymer and an aqueous polyurethane dispersion. The mixture comprises from 10 wt% to 70 wt%, or from 20 wt% to 60 wt%, or from 30 wt% to 50 wt% of the aqueous polyurethane dispersion. In further non-limiting embodiments, the mixture comprises from 30 wt% to 90 wt%, or from 40 wt% to 80 wt%, or from 50 wt% to 70 wt% of the aqueous solution of the cationic nitrogen-containing polymer. The weight percentages are based on the total weight of the microporous substrate coating composition.

In one non-limiting embodiment of the invention, water may be added to the mixture of the cationic nitrogen-containing polymer and the polyurethane. When water is added to the mixture, the resulting microporous substrate coating composition contains from 1 wt% to 35 wt%, or from 1 wt% to 20 wt%, or from 1 wt% to 10 wt% total resin solids, based on the total weight of the microporous substrate coating composition. When the total resin solids are too high, the viscosity of the coating composition may be such as to result in poor penetration of the coating composition. When the total resin solids are too low, the viscosity of the coating composition may be such that poor application to the substrate results. In one non-limiting embodiment, the coating composition of the present invention has a viscosity of less than 500cps, or less than 400cps when tested using a Brookfield viscometer (RVT, spindle No.1, 50rpm at 25 ℃); and at least 10cps, or at least 25 cps. While the viscosity can vary outside of the above ranges, a viscosity within the above ranges allows the coating composition to wet the substrate while maintaining the degree of porosity in the final coated substrate.

In one non-limiting embodiment, the coating composition used in the present invention includes a co-solvent. Any co-solvent known in the art may be used. Non-limiting examples of suitable co-solvents include lower alkyl alcohols, n-methyl pyrrolidone, Dowanol PM, toluene, and glycol ethers.

The coating composition for the microporous substrate of the present invention may include other additives typically known in the art. Non-limiting examples of such additives include surfactants such as nonionic, cationic, anionic, amphoteric surfactants; rheology modifiers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, natural and synthetic resins; insecticides such as blends of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one available under the tradename Kathon from Rohm and Haas co, 2-hydroxypropyl methane thiosulfonate, and dithiocarbamates; and coupling agents, such as titanium, silane type, trisodium pyrophosphate.

While the pH of the coating composition of the present invention may vary, in additional non-limiting embodiments, the pH of the coating composition is less than 7, or less than 6, or less than 5. When the pH is outside of these ranges, the cationic polymeric dye fixative material may not carry sufficient cationic charge to perform its desired function. Further, when the pH is within the above range, the wetting action of the coating composition can be improved. In one non-limiting embodiment, the coating composition has a pH greater than 2.

The coating composition can be prepared by known methods in microporous substrates. In one non-limiting embodiment of the invention, a substrate coating composition is prepared by a process comprising: an aqueous solution of a cationic nitrogen-containing polymer is added to an aqueous polyurethane dispersion. Sufficient mixing was maintained during the addition to ensure a homogeneous mixture. It has been observed that when aqueous anionic polyurethane dispersions are added to aqueous solutions of cationic nitrogen-containing polymers, coagulation occurs and a homogeneous mixture cannot be obtained.

The coating composition used in the present invention can be applied to an ink jet recordable substrate using any method known in the art. In one non-limiting embodiment, the method comprises:

(a) providing a microporous substrate having a top surface and a bottom surface;

(b) providing the above-described coating composition; and

(c) at least partially applying the coating composition to at least one surface of the microporous substrate.

The thickness of the at least partially coated microporous substrate may vary. In further non-limiting embodiments of the invention, the at least partially coated microporous substrate has a thickness of at least 2.54 micrometers (0.1 mil), or from 12.7 micrometers to 2.54 millimeters (0.5 to 100 mils), or from 25.4 micrometers to 1.27 millimeters (1 to 50 mils), or in some cases from 101.6 micrometers to 355.6 micrometers (4 to 14 mils). When the thickness of the at least partially coated microporous substrate exceeds the above range, it may not be possible to properly pass through an ink jet printer. When the at least partially coated microporous substrate is below the stated range, it may not have sufficient strength for its intended use.

Any method known in the art can be used to apply the coating composition to the microporous substrate, such as flexographic printing, spray coating, air knife coating, curtain coating, dipping, rod coating, knife coating, gravure printing, reverse roll coating, impregnation, sizing squeeze, printing, brush coating, draw coating, slot die coating, and extrusion.

After application of the coating composition to the substrate, the solvent is removed from the applied coating by any conventional drying technique. In one non-limiting embodiment, the coating is dried by exposing the substrate to a temperature of from ambient temperature to 176.7 ℃ (350 ° F).

The coating composition may be at least partially applied at least once to at least one surface of the substrate. When the coating composition is applied more than once, the applied coating is typically, but not necessarily, partially or completely dried between coating applications.

When the coating composition is at least partially applied to a microporous substrate, in one non-limiting embodiment, the coating composition may at least partially penetrate into the substrate. At least partial penetration of the coating into the microporous substrate can improve the quality of ink jet printing on the coated substrate. In one non-limiting embodiment, the coating can at least partially penetrate at least the first one (1) micron of the surface of the microporous substrate. In further non-limiting embodiments, the coating may at least partially penetrate at least the first ten (10) microns, or at least the first twenty (20) microns or at least the first thirty (30) microns of the microporous substrate.

The coating composition can be applied to the substrate by a variety of known techniques. In one non-limiting embodiment of the invention, air knife coating techniques may be used, wherein the coating composition is applied to the substrate by "blowing" off excess coating from a forceful jet of air knives. In another non-limiting embodiment, a reverse roll coating process is used. In this method, the coating composition is metered onto the coater roll by precise setting of the gap between the upper metering roll and the application roll below it. The coating is wiped from the applicator roll by the substrate as it passes near the bottom backing roll.

In another non-limiting embodiment of the invention, gravure coating can be used to apply the coating composition. In the gravure coating process, an engraved roll is moved in a coating bath, which fills the engraved dots or lines of the roll with the coating composition. Any excess coating on the roll is wiped off by a scalpel blade and the coating composition is deposited onto the substrate as it passes between the engraved roll and the pressure roll. A reverse gravure coating method may be used. In this method, the coating composition is metered from the engraving on the roll before being wiped off as in a conventional reverse roll coating process.

In a further non-limiting embodiment, the metering bar may be used to apply the coating composition. When a metering bar is used, excess coating is deposited onto the substrate as it passes through the bath roller. The wire-wound metering rod, sometimes referred to as a Meyer Bar coater, allows the desired amount of coating to remain on the substrate. The number is determined by the diameter of the wire used in the rod.

The amount of substantially dry coating applied to a substrate, or "coat weight", is typically measured as the weight of coating per coated area. The coating weight can vary widely. In another non-limiting embodiment, it may be at least 0.001g/m²Or at least 0.01g/m²And in some cases at least 0.1g/m². In a further non-limiting embodiment, the coating weight is no greater than 50g/m²Or not more than 40g/m²And in some cases no greater than 35g/m². The coating weight may vary between any of the amounts.

In non-limiting embodiments, the substantially dry coating includes 10 to 70 weight percent, or 20 to 60 weight percent, and in some cases 30 to 55 weight percent of the polyurethane and 30 to 90 weight percent, or 40 to 80 weight percent, and in some cases 45 to 75 weight percent of the nitrogen-containing polymer of the coating. The amount of each component in the substantially dry coating can be determined from the amount of each component used to prepare the coating composition.

As used herein and in the claims, "substantially dry" is used to mean a coating that feels dry to the touch.

The microporous substrate can be printed using a wide variety of printing inks and using a wide variety of printing processes. Both printing inks and printing processes are conventional per se and known in the art. In a non-limiting embodiment, the microporous substrate of the present invention may be used as an ink jet printable recording substrate for ink jet printing. Printing may be done prior to assembly of the microporous material into the multilayer articles of the present invention, or after assembly of such multilayer articles.

In the present invention, a substantially water-resistant, at least partially coated microporous substrate is attached to at least one application of a substantially non-porous material. The term "substantially non-porous material" as used herein and in the claims means a material that is generally impermeable to liquids, gases, or bacteria. On a visual scale, a substantially non-porous material exhibits few, if any, pores. As previously mentioned, the term "pore" as used herein and in the claims means a tiny opening through which a substance passes. The substantially non-porous materials used in the present invention may vary widely and may include those materials that are commonly recognized and employed for their known barrier properties. Non-limiting examples of such materials include substantially non-porous thermoplastic polymers, substantially non-porous metallized thermoplastic polymers, substantially non-porous thermoset polymers, substantially non-porous elastomers, and substantially non-porous metals. The substantially non-porous material may be in the form of a sheet, film, or foil, or other shapes that may be used when desired, such as plates, strips, rods, tubes, and more complex shaped forms. In one non-limiting embodiment, the substantially non-porous material used in the present invention may be in the form of a sheet, film or foil.

The term "thermoplastic polymer" as used herein and in the claims means a polymer that can be softened by heat and regains its original properties when cooled. The term "thermoset polymer" as used herein and in the claims means a polymer that cures or sets and cannot be remelted upon heating.

Non-limiting examples of suitable thermoplastic polymer materials include polyethylene, high density polyethylene, low density polyethylene, polypropylene, poly (vinyl chloride), saran, polystyrene, high impact polystyrene, nylon, polyesters such as poly (ethylene terephthalate), copolymers of ethylene and acrylic acid, copolymers of ethylene and methacrylic acid, and mixtures thereof. If desired, all or part of the carboxyl groups of the carboxylic acid-containing copolymer may be neutralized with sodium, zinc, or the like. A non-limiting example of a metallized thermoplastic polymer material is aluminized poly (ethylene terephthalate).

Non-limiting examples of thermosetting polymers include thermosetting phenol-formaldehyde resins, thermosetting melamine-formaldehyde resins, and mixtures thereof.

Non-limiting examples of elastomeric materials include natural rubber, neoprene, styrene-butadiene rubber, acrylonitrile-butadiene-styrene rubber, elastomeric polyurethanes, elastomeric copolymers of ethylene and propylene.

Non-limiting examples of metals include iron, steel, copper, brass, bronze, chromium, zinc, die metal, aluminum, and cadmium. The most commonly employed metals are alloys and the thermosetting polymers useful in the present invention include a wide variety of polymers known in the art.

The multilayer articles of the present invention can be constructed using a number of known methods of joining at least one layer of a microporous substrate to at least one layer of a substantially non-porous material. In one non-limiting embodiment, at least one layer of a substantially water-resistant, at least partially coated microporous substrate may be melt bonded to at least one layer of a substantially non-porous material. Microporous substrates generally include opposing major surfaces that are characteristic of sheets, films, foils, and plates. The resulting multilayer article may comprise one or more layers of a microporous substrate and one or more layers of a substantially non-porous material. In one non-limiting embodiment, at least one of the exterior layers is a microporous substrate. In a further non-limiting embodiment, the microporous substrate can be an ink jet recordable substrate.

In one non-limiting embodiment, the multilayer articles of the present invention can be produced by melt bonding in the absence of an adhesive. Fusion bonding can be accomplished using conventional techniques, such as by using a seal as follows: heated rolls, heated rods, heated plates, heated belts, heated wires, flame bonding, Radio Frequency (RF) sealing, and ultrasonic sealing. Solvent bonding may be used wherein the substantially non-porous substrate is at least partially dissolved in the applied solvent to the extent that the surface becomes tacky. It is possible to contact the microporous substrate with a tacky surface and then remove the solvent to form a melt bond. In a non-limiting embodiment, the foamable composition can be foamed in contact with a microporous substrate to form a melt bond between the foam and the substrate. A film or sheet of non-porous substrate may be extruded while still hot and tacky and contacted with the microporous substrate to form a melt bond. The melt bonding may be permanent or peelable, depending on the known bonding technique and/or the nature of the substantially non-porous substrate employed.

In one non-limiting embodiment, heat sealing is used to melt bond the microporous substrate to the substantially non-porous material. Typically, heat sealing involves inserting the microporous substrate into standard heat sealing equipment known in the art. In one non-limiting embodiment, the microporous substrate is inserted in combination with a substantially non-porous material, which may be a thermoplastic and/or thermoset polymer. Heat and/or pressure may be applied to the substrate/polymer construction for a period of time. The amount and length of time of the heat and/or pressure may vary widely. In general, the temperature, pressure, and time are selected such that the substrate and polymer are at least partially joined together to form a multilayer article. Typical temperatures can range from 37.8 deg.C to 204.4 deg.C (100 deg.F to 400 deg.F). Typical pressures may range from 5psi to 250psi, and typical times may range from one (1) second to thirty (30) minutes. The multi-layer article may then be simultaneously cooled under pressure for a typical time, such as thirty (30) minutes. Although the strength of the bond formed between the substrate and the polymer may vary, the strength may be such that it generally exceeds the tensile properties of the substrate alone.

In one non-limiting embodiment, the substantially non-porous substrate may be polyvinyl chloride.

In one non-limiting embodiment, microporous substrates useful in the present invention can be at least partially attached to non-porous substrates such as polyethylene and polypropylene by heat sealing in the absence of an extraneous adhesive. The melt bond obtained is generally strong enough, which is surprisingly comparable to the lamination of materials to polyolefins (which is often difficult) that cannot be obtained unless special adhesives are used.

In one non-limiting embodiment, the microporous substrate may be substantially continuously at least partially attached to the substantially non-porous material, or it may be intermittently at least partially attached to the substantially non-porous material. Non-limiting examples of discontinuous bands include bond regions of the form: one or more dots, spots, stripes, serrations, undulating stripes, meandering stripes, open line stripes, closed line stripes, irregular areas, etc. In further non-limiting embodiments, when referring to a pattern of bonding, they can be random, repeating, or a combination of both.

In another non-limiting embodiment, the microporous substrate may be attached to the substantially non-porous material under an adhesive. The adhesive used in the present invention may be selected from a wide variety of adhesives known in the art. Non-limiting examples of suitable binders include those having sufficient molecular weight and viscosity such that the binder does not substantially migrate into or penetrate the microporous substrate. Migration or penetration of the adhesive into the substrate can reduce the tack and bond strength of the adhesive. Non-limiting examples of suitable adhesives for use in the present invention include, but are not limited to, polyvinyl acetate, starch, gums, polyvinyl alcohol, animal glue, acrylic adhesives, epoxy adhesives, polyethylene containing adhesives, and rubber containing adhesives. The adhesive may be applied to the substrate, or to the substantially non-porous material, or to both the substrate and the substantially non-porous material. In addition, the binder may be incorporated by using a transitional washcoat.

The method of bonding the substrate and the substantially non-porous material in the presence of the adhesive includes inserting the substrate/adhesive/material construction into standard processing equipment known in the art. Heat and/or pressure may be applied to the substrate/adhesive/material construction for a certain period of time. The amount and length of time of the heat and/or pressure may vary widely. In general, the temperature, pressure, and time are selected such that the substrate and the substantially non-porous material are at least partially joined together to form a multilayer article. Typical temperatures can range from 37.8 deg.C to 204.4 deg.C (100 deg.F to 400 deg.F). Typical pressures may range from 5psi to 250psi, and typical times may range from one (1) second to thirty (30) minutes. The multi-layer article may then be cooled under pressure for a typical time, such as thirty (30) minutes. Although the strength of the bond formed between the porous substrate and the substantially non-porous material may vary, the strength may generally be such that it typically exceeds the tensile properties of the substrate alone.

In one non-limiting embodiment of the invention, the microporous substrate may be molded using conventional molding techniques known in the art. The substrate may be molded in the presence or absence of a substantially non-porous material, such as a thermoplastic and/or thermoset polymer. Typically, the microporous substrate is inserted into standard molding equipment known in the art. In one non-limiting embodiment, a thermoplastic and/or thermoset polymer is introduced onto the substrate and then the substrate/polymer construction is inserted into the mold cavity. In another non-limiting embodiment, the substrate is placed into a mold cavity and then the thermoplastic and/or thermoset polymer is introduced onto the substrate. Heat and/or pressure may be applied to the substrate/polymer construction for a period of time. The amount and length of time of the heat and/or pressure may vary widely. In general, the temperature, pressure, and time are selected such that the substrate and polymer are at least partially joined together to form a multilayer article. Typical temperatures can range from 37.8 deg.C to 204.4 deg.C (100 deg.F to 400 deg.F). In non-limiting embodiments, wherein the polymer comprises a thermoplastic polymer, the substrate/polymer construction can be heated to a temperature equal to or exceeding the melting temperature of the thermoplastic polymer. In one non-limiting embodiment, where the thermoplastic polymer may be amorphous, the substrate/polymer construction may be heated to a temperature equal to or exceeding the vicat temperature. In additional non-limiting embodiments, wherein the polymer comprises a thermoset polymer, the temperature may be less than the curing or crosslinking temperature of the polymer. Typical pressures may range from 5psi to 250psi, and typical times may range from one (1) second to fifteen (15) minutes. The result of a typical molding process is the reshaping of the original article. Reshaping is generally determined by the design of the mold cavity. Thus, in a standard molding process, a two-dimensional flat sheet can be reformed into a three-dimensional article.

In one non-limiting embodiment of the invention, the microporous substrate comprises Teslin, which is available from PPG Industries, Incorporated of Pittsburgh, Pa. The thickness of the microporous substrate of the present invention varies widely depending on the application used. In one non-limiting embodiment, the microporous substrate may be 127 micrometers to 508 micrometers (5 to 20 mils) thick.

In general, the multilayer articles of the present invention can be produced using a variety of molding and lamination procedures known in the art including, but not limited to, compression molding, rotational molding, injection molding, calendering, roll/nip calendering, thermoforming, vacuum forming, extrusion coating, continuous belt lamination, and extrusion lamination.

In one non-limiting embodiment, other transitional coatings known in the art can be used in conjunction with the substrate and the substantially non-porous material.

The multilayer articles of the present invention have many and varied uses including seaming, joining, and sealing of gaskets, pad assemblies, markers, cards, printed substrates, substrates for pen and ink drawing, maps (particularly maritime maps), book covers, printed paper, wall coverings, and breathable packages.

The multilayer articles of the present invention can be used for the purpose of decorating or identifying the substantially non-porous material, or imparting unique properties to the surface of the substrate to the substantially non-porous material. Various methods can be employed to decorate an ink jet recordable substrate including: offset/lithographic printing, flexographic printing, painting, gravure printing, inkjet printing, electrophotographic printing, sublimation printing, thermal transfer printing, and screen printing. Decoration may also include applying a single or multiple layer coating to the ink jet recordable substrate by normal application methods known in the art. In general, unique properties that an ink jet recordable substrate can impart on a substantially non-porous material include, but are not limited to, one or more of the following: improved surface energy, increased porosity, reduced porosity, increased bond strength of the post-coating, and improvement in the texture or pattern of the polymer surface.

Polymer processing techniques are disclosed in U.S. patent No.4,892,779, which is incorporated herein by reference.

The present invention is more particularly described in the following examples that are intended for the purpose of illustration only, since numerous modifications and variations therein will be apparent to those skilled in the art. All parts and percentages are by weight unless otherwise indicated.

Examples

Example 1 thermal lamination

A sheet of TS 1000 (available from PPG Industries, Incorporated under the trade name Teslin) having dimensions of 215.9 x 279.4 millimeters (8.5 x 11 inches) was cut from the master roll. Teslin sheets were coated using four (4) passes on each side. A coating composition for coating Teslin was prepared by: a 31% solids anionic polyurethane under the trade name WitcoBond 234 (available from Crompton Corporation, Greenwich, Connecticut) was first diluted to 12.3% solids in a stainless steel mixing tank with high speed mixing using an overhead mixer. In a separate feed tank, a 55% solids solution of polyamidoamine reacted with dimethylamine and epichlorohydrin (available under the trade name CinFix NF from Stockhausen GmbH & co.kg, Krefeld, germany) was diluted to 7.7% solids and then subsequently added to the diluted anionic polyurethane dispersion at 50/50 volume ratio and the mixture was mixed for 15 minutes. The pH is adjusted to 5.0 +/-0.5. The total resin solids of the mixture was 10%.

The coating composition was applied to Teslin sheeting (254 micrometers (10 mils) thick) using a flexographic coating technique that included two coating stations containing forced air drying ovens. Each coating station consists of a coating feed chamber, an ink transfer roller and a rubber roller. The paint feed chamber is supplied from a paint holding tank and a pump. There is only one coating station for the preparation of this material. The apparatus was equipped with a 7bcm (billion cubic microns) ink transfer roller, line speed was 180fpm (feet per minute), and oven temperature was 105 ℃ (220 ° F). Eight (8) passes per roll were made, which corresponds to four (4) passes per surface.

The test prints were printed onto the sheets using an HP1220C color inkjet printer. The printed sheets were laminated using the following lamination peel strength test method. A215.9X 279.4 mm (8.5X 11 inch) piece of Teslin was covered with a 215.9X 279.4 mm (8.5X 11 inch) Sealtran3/2 laminate film. A 50.8 x 279.4 mm (2 x 11 inch) strip of 20 pound file paper (bond paper) was placed on Teslin along the center line (in the 279.4 mm (11 inch) direction). The film to be tested was cut to 215.9 x 279.4 mm (8.5 inches by 11 inches) and placed directly on top of the above structure. The laminate was cut into 107.95 x 279.4 mm (4.25 inches by 11 inches) pieces. The strips (25.4X 107.95 mm) (1 inch by 4.25 inches) were then cut using a JDC Precision sample cutter (twisting Albertinstruments). Each strip was placed in a silicone-coated "lamination pocket". The bags are fed through a bag laminator large enough to accommodate the bags. The range of temperature variation of the laminating roller is 275 ℃ C. and 300 ℃ F. (120 ℃ C. and 135 ℃ C.). The laminated samples were then stored at room temperature for at least 24 hours prior to peel testing. The laminate film was peeled back from the Teslin and placed in the top jaw of a tensile tester. The bottom portion was placed into the bottom jaw of the tensile tester. 180 ° peel was performed at 12.7 mm (0.5 inch)/minute with a sample rate of 4.0 pt./sec. The test results showed an initial peel strength of 9.6 lbs/inch and showed that the resulting substrate retained its integrity after 24 hours of water immersion.

Example 2 thermal lamination

TS 1000 sheets measuring 215.9X 279.4 mm (8.5X 11 inches) were cut from a Teslin master roll. Teslin was applied using two (2) passes on each side. A coating composition for coating Teslin was prepared using a high shear coating procedure. 61.5 aliquots of witcobond 234 at 31% solids in water were added to 38.5 aliquots of CinFix NF at 52% solids in water at a controlled rate under high shear mixing. The resultant Witcobond 234/cifix NF mixture was reduced to a final mixture of 10% solids by adding water at a controlled rate while continuing high shear mixing. The procedure used to apply this coating composition to Teslin was the same as that used in example 1. Three test patterns (supplied by HP) were printed on the coated Teslin sheet using an HP1220 ℃ colour inkjet printer. The printed sheets were then laminated using the same procedure as described in example 1, except that the bag laminate temperature was 107 ℃ (225 ° F) and Transilwrap 7/3 KRTY polyester was used as the laminating film. The laminate was then die cut into 70ISO 7810ID-1 cards. The cards show good integrity when laminated. No quantitative test was performed.

Example 3 Hydraulic Press plate lamination

TS 1000 sheets measuring 355.6X 355.6 mm (14X 14 inch) were cut from a Teslin master roll. Teslin was applied with two (2) passes (2 x 2) on each side using the same coating composition used in example 2 and the same flexographic application technique used in example 1. The coated Teslin sheet was then placed on top of two 355.6 x 355.6 mm (14 x 14 inch) sheets of 0.254 mm (0.010 inch) polyvinyl chloride (PVC) supplied by Empire Plastics. This construct was placed into a Technical Machine Products (TMP) laminator. The composite construction was compression laminated at a temperature of 93.3 ℃ (200 ° F) for 10 minutes at 200psi pressure. After lamination, ISO7910ID-1 cards were die cut from the completed 355.6 x 355.6 millimeter (14 x 14 inch) construction. The finished cards had good integrity, and any attempt to delaminate them damaged the Teslin layer, which demonstrated good bonding between Teslin and PVC in the absence of adhesive.

Example 4 Hydraulic Press plate lamination

Teslin was coated in two (2) passes (2 x 2) on each side using the same coating composition used in example 2 and the same flexographic coating technique used in example 1 for coating, using TS 1000 pieces having dimensions of 355.6 x 355.6 mm (14 x 14 inches) cut from a master roll of Teslin. The coated Teslin sheet was then placed on top of a 0.254 mm (0.010 ") thick 355.6 x 355.6 mm (14 inch x 14 inch) PVC sheet (provided by Empire Plastics) and a 0.381 mm (0.015") thick 355.6 x 355.6 mm (14 x 14 inch) PVC sheet. The construct was placed in a Technical Machine Products (TMP) laminator. The composite construction was compression laminated at a temperature of 85 ℃ (185 ° F) for 10 minutes at a pressure of 175 psi. After lamination, ISO7910ID-1 cards were die cut from the completed 355.6 x 355.6 millimeter (14 x 14 inch) construction. The finished cards had good integrity, and any attempt to delaminate them damaged the Teslin layer, which demonstrated good bonding between Teslin and PVC in the absence of adhesive.

Example 5 Hydraulic Press plate lamination

Teslin was coated in two (2) passes (2 x 2) on each side using the same coating composition used in example 2 and the same flexographic coating technique used in example 1 for coating, using TS 1000 pieces having dimensions of 355.6 x 355.6 mm (14 x 14 inches) cut from a master roll of Teslin. The coated Teslin sheet was then placed on top of a 0.254 mm (0.010 ") thick 355.6 x 355.6 mm (14 inch x 14 inch) PVC sheet (provided by Empire Plastics) and a 0.381 mm (0.015") thick 355.6 x 355.6 mm (14 x 14 inch) PVC sheet. This construct was placed into a Technical Machine Products (TMP) laminator. The composite construction was compression laminated at a temperature of 85 ℃ (185 ° F) for 5 minutes at a pressure of 175 psi. After lamination, ISO7910ID-1 cards were die cut from the completed 355.6 x 355.6 millimeter (14 x 14 inch) construction. The finished cards had good integrity, and any attempt to delaminate them damaged the Teslin layer, which demonstrated good bonding between Teslin and PVC in the absence of adhesive.

Example 6 Hydraulic Press plate lamination

Teslin was coated in two (2) passes (2 x 2) on each side using the same coating composition used in example 2 and the same flexographic coating technique used in example 1 for coating, using TS 1000 pieces having dimensions of 355.6 x 355.6 mm (14 x 14 inches) cut from a master roll of Teslin. The coated Teslin sheet was then placed on top of a 0.254 mm (0.010 inch) thick 355.6 x 355.6 mm (14 inch x 14 inch) PVC sheet (provided by Empire Plastics) and a 0.381 mm (0.015 inch) thick 355.6 x 355.6 mm (14 x 14 inch) PVC sheet. This construct was placed into a Technical Machinery Products (TMP) laminator. The composite construction was then compression laminated at a temperature of 79.4 ℃ (175 ° F) for 4 minutes at a pressure of 175 psi. After lamination, ISO7910ID-1 cards were die cut from the completed 355.6 x 355.6 millimeter (14 x 14 inch) construction. The finished cards were then separated, which showed a lack of good bonding between Teslin and PVC.

Example 7-Hydraulic Press plate lamination (one composite sheet/book)

Teslin sheets having dimensions of 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick were cut from the master roll in the grain length direction. Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. The coated Teslin sheet was placed on top of a 577.85 x 704.85 mm (22.75 x 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 50.8 micron (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 x 30 inches) was placed on a Teslin sheet to serve as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 mm x 762 mm x 3.175 mm (24 inch x 30 inch x 125 mil) polished stainless steel metal plates. This entire construct was placed into a 200-TonWabash laminator preheated to 121 ℃ (250 ° F). The composite construction was compression laminated at a temperature of 121 ℃ (250 ° F) for 12 minutes at a pressure of 175 psi. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 20 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 577.85 x 704.85 x 0.7366 mm (22.75 inches x 27.75 inches x 29.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 8-Hydraulic Press plate lamination (two composite sheets/book)

Teslin sheets measuring 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick of the treated Teslin substrate were cut in the grain length direction from the master roll. Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. The coated Teslin sheet was placed on top of a 577.85 x 704.85 mm (22.75 x 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 x 762 x 3.175 mm (24 inches x 30 inches x 125 mils) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This entire construct was placed into a 200-TonWabash laminator preheated to 121 ℃ (250 ° F). The composite construction was compression laminated at a temperature of 121 ℃ (250 ° F) for 12 minutes at a pressure of 175 psi. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 20 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.7366 mm (22.5 inches × 27.5 inches × 29.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 9-Hydraulic Press plate lamination (four composite sheets/book)

Teslin sheets having dimensions of 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick were cut from the master roll in the grain length direction. Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. The coated Teslin sheet was placed on top of a 577.85 x 704.85 mm (22.75 x 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 x 762 x 3.175 mm (24 inches x 30 inches x 125 mils) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated twice so that there are four (4) pre-pressed multi-ply plies in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 121 ℃ (250 ° F). The composite construction was compression laminated at a temperature of 121 ℃ (250 ° F) for 12 minutes at a pressure of 175 psi. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 20 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.7366 mm (22.5 inches × 27.5 inches × 29.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 10 Hydraulic Press plate lamination (four composite sheets/book)

Teslin sheets having dimensions of 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick were cut from the master roll in the grain length direction. Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. The coated Teslin sheet was placed on top of a 577.85 x 704.85 mm (22.75 x 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 x 762 x 3.175 mm (24 inches x 30 inches x 125 mils) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated twice so that there are four (4) pre-pressed multi-ply plies in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 121 ℃ (250 ° F). The composite construction was compression laminated at a temperature of 121 ℃ (250 ° F) for 10 minutes at a pressure of 175 psi. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 20 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.7366 mm (22.5 inches × 27.5 inches × 29.0 mils) composite sheet. The finished card had good integrity and good iat flatness. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 11-Hydraulic Press plate lamination (four composite sheets/book)

A 0.254 mm (10 mil) thick sheet of Teslin substrate was cut from the master roll in the grain length direction in the dimensions 577.85 x 704.85 mm (22.75 x 27.75 inches). Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. The coated Teslin sheet was placed on top of a 577.85 x 704.85 mm (22.75 x 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 x 762 x 3.175 mm (24 inches x 30 inches x 125 mils) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated twice so that there are four (4) pre-pressed multi-ply plies in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 135 ℃ (275 ° F). The composite construction was compression laminated at a temperature of 135 ℃ (275 ° F) for 8 minutes at 200psi pressure. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 22 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. An ISO7910ID-1 card was die cut from the resulting 571.5 x 698.5 x 0.7366 mm (22.5 inches x 27.5 inches x 29.0) mil composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 12-Hydraulic Press plate lamination (four composite sheets/book)

A 0.254 mm (10 mil) thick sheet of Teslin substrate was cut from the master roll in the grain length direction in the dimensions 577.85 x 704.85 mm (22.75 x 27.75 inches). Teslin was applied using the same coating composition and flexographic application technique described in example 1 with three (3) passes (3 x 3) on each side. A coated Teslin sheet was placed on top of a 577.85X 704.85 mm (22.75X 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. (note | the release liner was removed from the composite sheet after lamination and it was not an integral part of the final composite sheet.) this construction was placed between two 609.6 x 762 x 3.175 mm (24 inch x 30 inch x 125 mil) polished stainless steel metal plates. The same polyester/coated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated two additional times so that there are four pre-pressed multi-ply layers in the stack. This entire construct was placed into a 200-TonWabash laminator preheated to 135 ℃ (275 ° F). The composite construction was compression laminated at a temperature of 135 ℃ (275 ° F) for 6 minutes at 200psi pressure. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 22 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.7366 mm (22.5 inches × 27.5 inches × 29.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 13-Hydraulic Press plate lamination (four composite sheets/book) -failure

A 0.254 mm (10 mil) thick sheet of Teslin substrate was cut from the master roll in the grain length direction in the dimensions 577.85 x 704.85 mm (22.75 x 27.75 inches). Teslin was applied using the same coating composition and flexographic application technique described in example 1 with three (3) passes (3 x 3) on each side. A coated Teslin sheet was placed on top of a 577.85X 704.85 mm (22.75X 27.75 inch) sheet of 0.508 mm (0.020 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. (note | the release liner was removed from the composite sheet after lamination and it was not an integral part of the final composite sheet.) this construction was placed between two 609.6 x 762 x 3.175 mm (24 inch x 30 inch x 125 mil) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. This pattern is repeated two additional times so that there are four pre-pressed multi-ply layers in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 135 ℃ (275 ° F). The composite construction was compression laminated at a temperature of 135 ℃ (275 ° F) for 4 minutes at 200psi pressure. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 20 minutes. After removal from the press, all four compacts were removed from the book. The Teslin/PVC sheet was peeled apart indicating a lack of bond strength. No attempt was made to manufacture ISO7910ID-1 cards.

Example 14-Hydraulic Press plate lamination (four composite sheets/book)

Teslin sheets having dimensions of 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick were cut from the master roll in the grain length direction. Teslin was applied using the same coating composition and flexographic application technique described in example 2 with three (3) passes (3 x 3) on each side. A coated Teslin sheet was placed on top of a 577.85X 704.85 mm (22.75X 27.75 inch) sheet of 0.6096 mm (0.024 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. (note | the release liner was removed from the composite sheet after lamination and it was not an integral part of the final composite sheet.) this construction was placed between two 609.6 x 762 x 3.175 mm (24 inch x 30 inch x 125 mil) polished stainless steel metal plates. The same polyester/coated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated twice so that there are four pre-pressed multi-ply plies in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 135 ℃ (275 ° F). The composite construction was compression laminated at a temperature of 135 ℃ (275 ° F) for 8 minutes at 200psi pressure. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 22 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.8382 mm (22.5 inches × 27.5 inches × 33.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Example 15 Hydraulic Press plate lamination (four composite sheets/book)

Teslin sheets having dimensions of 577.85 x 704.85 mm (22.75 x 27.75 inches), 0.254 mm (10 mils) thick were cut from the master roll in the grain length direction. Teslin was applied using the same coating composition and flexographic application technique described in example 1 with three (3) passes (3 x 3) on each side. A coated Teslin sheet was placed on top of a 577.85X 704.85 mm (22.75X 27.75 inch) sheet of 0.6096 mm (0.024 inch) polyvinyl chloride (Klockner PVC280/09 copolymer). The PVC sheet was cut in the grain length direction. A 0.0508 millimeter (2 mil) clear polyester sheet having dimensions 609.6 x 762 millimeters (24 inches x 30 inches) was placed on the Teslin sheet as a release liner. The release liner is removed from the composite sheet after lamination and is not part of the final composite sheet. This construction was placed between two 609.6 x 762 x 3.175 mm (24 inches x 30 inches x 125 mils) polished stainless steel metal plates. The same polyester/treated Teslin sheet/PVC lay-up was placed on top of the stainless steel plate from the existing construction. The polished metal plate was placed on the exposed polyester release liner. This pattern is repeated two additional times so that there are four pre-pressed multi-ply layers in the stack. This entire construct was placed into a 200-Ton Wabash laminator preheated to 135 ℃ (275 ° F). The composite construction was compression laminated at a temperature of 135 ℃ (275 ° F) for 6 minutes at 200psi pressure. While under pressure, the platens were cooled to less than 37.8 ℃ (100 ° F), which took about 22 minutes. After removal from the press, the resulting composite sheet is removed from the stacked construction. The finished composite sheet had good integrity, any attempt to delaminate damaged the Teslin layer, which exhibited good adhesion and a seamless bond between Teslin and PVC. ISO7910ID-1 cards were die cut from the obtained 571.5 × 698.5 × 0.8382 mm (22.5 inches × 27.5 inches × 33.0 mils) composite sheet. The finished card has good integrity and good lat plane. Any attempt to delaminate damages the Teslin layer, which exhibits good adhesion and a seamless bond between Teslin and PVC.

Claims (33)

1. A multilayer article comprising a microporous substrate at least partially attached to a substantially nonporous material, the microporous substrate being at least partially coated with a substantially water resistant coating composition comprising a stable dispersion of:

(a) an aqueous polyurethane dispersion; and

(b) a cationic nitrogen-containing polymeric dye fixative material at least partially soluble in an aqueous medium.

2. The multilayer article of claim 1, wherein the microporous substrate comprises:

(a) a polyolefin;

(b) a particulate silica material; and

(c) pores, wherein pores constitute at least 35% by volume of the microporous substrate.

3. The multilayer article of claim 2 wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and mixtures thereof.

4. The multilayer article of claim 3 wherein the polyethylene comprises a substantially linear high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters/gram and the polypropylene comprises a substantially linear high molecular weight polypropylene having an intrinsic viscosity of at least 5 deciliters/gram.

5. The multilayer article of claim 2, wherein the particulate silica material comprises precipitated silica.

6. The multilayer article of claim 2 wherein said particulate silica material comprises 50 to 90 weight percent of said microporous substrate.

7. The multilayer article of claim 2 wherein said pores comprise from 35% to 95% by volume of said microporous substrate.

8. The multilayer article of claim 1 wherein the aqueous polyurethane dispersion is selected from the group consisting of aqueous dispersions of anionic polyurethanes, cationic polyurethanes, nonionic polyurethanes, and mixtures thereof.

9. The multilayer article of claim 8 wherein the anionic polyurethane is selected from the group consisting of aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, aliphatic polycaprolactam polyurethanes, and mixtures thereof.

10. The multilayer article of claim 1, wherein the polymeric dye fixative material comprises a polymer comprising monomer residues derived from one or more nitrogen containing monomers selected from the group consisting of:

wherein R is¹Independently for each occurrence in each structure represents H or C₁-C₃An aliphatic group; r²Independently for each structure represents a group selected from C₂-C₂₀Divalent linking groups of aliphatic hydrocarbons, polyethylene glycol, and polypropylene glycol; r³H, C are represented independently for each case in each structure₁-C₂₂Aliphatic hydrocarbons or residues from the reaction of nitrogen with epichlorohydrin; z is selected from-O-or-NR⁴-, wherein R⁴Is H or CH₃(ii) a And X is halide or methylsulfate.

11. The multilayer article of claim 1, wherein the coating composition has a pH of less than 7.

12. The multilayer article of claim 1, wherein the microporous substrate comprises an ink jet recordable substrate.

13. The multi-layer article of claim 1, wherein the microporous substrate at least partially coated with the substantially water-resistant coating composition has a thickness of at least 2.54 microns.

14. The multilayer article of claim 1 wherein said substantially non-porous material is selected from the group consisting of substantially non-porous thermoplastic polymers, substantially non-porous metallized thermoplastic polymers, substantially non-porous thermoset polymers, substantially non-porous elastomers, substantially non-porous metals, and mixtures thereof.

15. The multilayer article of claim 14 wherein the thermoplastic polymer is selected from the group consisting of polyethylene, high density polyethylene, low density polyethylene, polypropylene, poly (vinyl chloride), saran, polystyrene, high impact polystyrene, nylon, polyester, copolymers of ethylene and acrylic acid, copolymers of ethylene and methacrylic acid, and mixtures thereof.

16. The multi-layer article of claim 14, wherein the thermosetting polymer is selected from the group consisting of thermosetting phenol-formaldehyde resins, thermosetting melamine-formaldehyde resins, and mixtures thereof.

17. The multi-layer article of claim 14, wherein the elastomer is selected from the group consisting of natural rubber, neoprene, styrene-butadiene rubber, acrylonitrile-butadiene-styrene rubber, elastomeric polyurethanes, elastomeric copolymers of ethylene and propylene, and mixtures thereof.

18. The multilayer article of claim 14 wherein the metal is selected from the group consisting of iron, steel, copper, brass, bronze, chromium, zinc, die metal, aluminum, cadmium, and mixtures thereof.

19. The multilayer article of claim 1, wherein said microporous substrate is at least partially attached to said substantially nonporous material by melt bonding in the absence of an adhesive.

20. The multi-layer article of claim 1, wherein the microporous substrate is at least partially attached to the substantially nonporous material by an adhesive.

21. The multi-layered article of claim 20, wherein the adhesive is polyvinyl acetate, starch, gum, polyvinyl alcohol, animal glue, acrylic adhesive, epoxy adhesive, polyethylene-containing adhesive, rubber-containing adhesive, and mixtures thereof.

22. A method of producing a multilayer article comprising the steps of:

(a) providing a microporous substrate having a top surface and a bottom surface;

(b) providing a substantially water-resistant coating composition comprising a stable dispersion of:

a. an aqueous polyurethane dispersion; and

b. a cationic nitrogen-containing polymeric dye fixative material at least partially soluble in an aqueous medium;

(c) at least partially applying the coating composition to at least one surface of the microporous substrate;

(d) at least partially attaching the microporous substrate of (c) to a substantially nonporous material.

23. The method of claim 22, wherein the microporous substrate comprises:

(a) a polyolefin;

(b) a particulate silica material; and

pores, wherein pores constitute at least 35% by volume of the microporous substrate.

24. The method of claim 23, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and mixtures thereof.

25. The process of claim 24 wherein the polyethylene comprises a substantially linear high molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters/gram and the polypropylene comprises a substantially linear high molecular weight polypropylene having an intrinsic viscosity of at least 5 deciliters/gram.

26. The method of claim 23, wherein the particulate silica material comprises precipitated silica.

27. The method of claim 22, wherein the microporous substrate comprises an ink jet recordable substrate.

28. The method of claim 22 wherein the aqueous polyurethane dispersion is selected from the group consisting of aqueous dispersions of anionic polyurethanes, cationic polyurethanes, nonionic polyurethanes, and mixtures thereof.

29. The method of claim 22, wherein the substantially non-porous material is selected from the group consisting of substantially non-porous thermoplastic polymers, substantially non-porous metallized thermoplastic polymers, substantially non-porous thermoset polymers, substantially non-porous elastomers, substantially non-porous metals, and mixtures thereof.

30. The method of claim 29, wherein the substantially non-porous material comprises polyvinyl chloride.

31. The method of claim 22, wherein the microporous substrate is at least partially attached to the substantially nonporous material by melt bonding in the absence of a binder.

32. The method of claim 22, wherein the microporous substrate is at least partially attached to the substantially nonporous material by an adhesive.

33. The method of claim 32, wherein the adhesive is polyvinyl acetate, starch, gum, polyvinyl alcohol, animal glue, acrylic adhesive, epoxy adhesive, polyethylene-containing adhesive, rubber-containing adhesive, and mixtures thereof.