WO2008115389A2

WO2008115389A2 - Inkjet recording media for metallic or semi-metallic images having a primarily inorganic micro porous ink-receptive layer that incorporates an ethylene imine polymer or copolymer

Info

Publication number: WO2008115389A2
Application number: PCT/US2008/003309
Authority: WO
Inventors: Asutosh Nigam
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-03-16
Filing date: 2008-03-12
Publication date: 2008-09-25
Anticipated expiration: 2009-09-16

Abstract

The present invention provides micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque primarily inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image. Any acceptable light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate that can accept at least one layer of the semi-opaque or opaque primarily inorganic ink receptive layer coating may be utilized as a base substrate layer. The ink-receptive layer is composed primarily of an inorganic layer such as silica or alumina hydrate that includes an effective amount of at least one polyethylene imine derivative polymer or copolymer and one or more optional cross-linker agents. The ink-receptive layer is a topcoat layer that may be optionally coated with a porous ink-transmitting layer. Further, the present invention provides micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image including a substrate basecoat or layer that is a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image substrate base at least partially coated with the micro porous ink-receptive coating layer.

Description

INKJET RECORDING MEDIA FOR METALLIC OR SEMI-METALLIC IMAGES HAVING A PRIMARLY INORGANIC MICRO POROUS INK-RECEPTIVE LAYER THAT INCORPORATES AN ETHYLENE EMINE POLYMER OR COPOLYMER

FIELD OF THE INVENTION The field of the present invention relates generally to micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque primarily inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image. Any acceptable light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate that can accept at least one layer of the semi- opaque or opaque primarily inorganic ink receptive layer coating may be utilized as a base substrate layer. The ink-receptive layer is composed primarily of an inorganic layer such as silica or alumina hydrate that includes an effective amount of at least one polyethylene imine derivative polymer or copolymer and one or more optional other polymers and cross-linker agents. The ink-receptive layer is a topcoat layer that may be optionally coated with a porous ink-transmitting layer. Further, the present invention provides micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image including a substrate basecoat or layer that is a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image substrate base at least partially coated with the micro porous ink-receptive coating layer.

BACKGROUND OF THE INVENTION There is a keen demand for substrates that meet high quality standards with respect to brightness, opacity, and dry and/or wet strength, and that, upon printing with any of a wide range of colorants, provide a water-resistant printed image. The ability of such substrates to yield a printed substrate having high resolution and clarity without bleeding or mottling of the image, even when using ink jet printing has become in very high demand. Also, such substrates need to have appropriately smooth or textured surfaces that can be easily received by a non-impact printing system and to avoid curling surfaces that can clog printing equipment. Customers further demand that such substrates be amenable to use with a variety of printing techniques, including not only conventional printing techniques, but also "impact free" printing techniques such as inkjet printing (particularly colored inkjet printing), laser printing, photocopying, and the like.

Further, there is a great demand for printable substrates having an opaque or semi- opaque outer layer on their surface that can be rendered clear or semi-opaque to produce a printed medium that is useful in advertising and/or for producing attractive labels on products. Particularly needed are printable substrates with high enough quality to be suitable for printing of a digital image with an ink-jet printer, wherein the outer layer of the substrate is capable of being rendered either semi-opaque or clear is constructed upon a clear, semi-opaque, colored, or a reflective substrate layer (such as a metallic looking reflective substrate layer, or a substrate layer having reflective metallic looking flakes or areas).

In one market area such substrates are particularly desired that have the ability to produce a metallic-looking image on the substrate, and perhaps even a holographic image. In another market area, there exists a need for clear base substrates with a printed image that can be used with a projector for presentations. Also, clear base substrates having an adhesive backing for applying to articles of commerce are particularly in demand. A particularly high demand is for holographic labeling, since this is very difficult and expensive to produce and can be in high demand if an appropriate quality label can be produced.

Published U.S. Patent application 2001/0051217 Al (hereinafter 51217 application) relates to a process for producing a light-emitting, glossy, reflective or metallic-looking image utilizing opaque coating compositions on a reflective, glossy, or luminescent substrate wherein the original surface of the substrate is initially masked but, after being contacted with a recording liquid, becomes transparent, revealing the glossy, reflective or luminescent substrate through the contacted, coated area. The opaque coating compositions are composed of a mixture of a polyacid and a polybase and may be used to treat a substrate either during or after manufacture. Substrates treated with the present opaque coating compositions can be used to yield high quality light-emitting, glossy, reflective, or metallic-looking images. However, quality control is required to avoid permanent finger prints when the recorded media is handled at higher temperatures and compositions must be carefully controlled to avoid cracking and peeling of the recorded coating layer from a metallic, foil or holographic substrate.

The above technology is based upon a coated inkjet receptor layer useful for inkjet photographic printing, which is based on a polymeric resin-type coating rather than on micro porous coatings. In such designs, at least one polymeric receiver swells to absorb the ink solvent vehicle, and inkjet dyes are fixed by cationic sites on the binder or on receiving layer additives. While resin-coated receivers offer many advantages, they also have some common shortcomings, including slow dry times, tackiness under high humidity conditions, and coating solubility or softening when exposed to water. In addition, at warmer temperatures the pressure from finger prints may leave permanent impressions on the printed media.

Micro porous coatings including gelatins have been utilized to try to eliminate some of the problems often associated with polymeric coatings in the glossy or matte photographic printable media, but not in semi-metallic, holographic, light-emitting or luminescent image media. While ink-receptive layers based upon micro porous coatings in glossy or matte inkjet media may have been helpful to eliminate or reduce many of the shortcomings of the polymeric coated media with regard to dry time, tackiness, and water sensitivity, many still suffer from significantly poorer performance in light-fastness and ozone-fastness. In addition, they generally have lower gloss and less ink density receptivity compared to resin coated media, and have not been utilized with any success in semi-metallic, holographic, light- emitting or luminescent printed media.

In general, the use of alumina hydrate or silica hydrate in micro porous inkjet receptive coatings is fairly well known in the art of matte and glossy photographic media. Early development of pigment based, or micro porous inkjet media focused on silica as the primary pigment. However, alumina hydrate possesses a positive (cationic) surface charge capable of forming a complex with anionic inkjet dyes, in addition to the physical characteristics that make silica so attractive. This combination of properties makes silica or alumina hydrate combinations particularly well-suited among pigments for high quality inkjet media applications.

Prior art coatings that use alumina hydrate out of necessity, or at least as a preferred component, rely primarily on PVOH or PVP as a binder since gelatin and alumina hydrate, particularly alumina hydrate of the boehmite structure, have limited compatibility. Such compatibility problems are well established and well documented in prior art patents. Often the high-speed coating operations such as blade coating, roll coating, and gravure coating would require several coating applications before achieving an effective coating thickness for an ink receptive layer.

In attempt to solve the above problems, ultra low molecular weight gelatins have been added to micro porous ink receptive layers, but such layers are still expensive and subject to cracking unless substantial cross-linking is done or a co-binder is added to fix the gelatin within the micro porous layer. In addition, a tricky balance of gelatin viscosity with cracking density must be found by mixing ultra low molecular weight gelatins with higher molecular weight gelatins. For example, see published U.S. patent application number 2004/0033323 Al for silica micro porous ink receptive layers including ultra low molecular weight gelatins imbedded in an alumina hydrate micro porous ink receptive layer to provide glossy photographic media useful for inkjet photographic printing.

Importantly, the lower the molecular weight of the gelatin, the more water soluble the gelatin is which can cause water fastness problems. Since ultra low molecular weight gelatins are water soluble they need to need to be bound to a cross-linker or a hardening agent must be used in order to avoid ultra low molecular weight gelatin leaching out of the media and presenting water fastness problems. Also, as of the molecular weight of the ultra low molecular weight gelatin is decreased it causes a corresponding increase in the amount of cracking problems for the surface of the media that includes a micro porous layer and the ultra low molecular weight gelatin. Thus, a tricky balance must be found for the use of higher weight gelatin incompatible with inorganic micro porous components in combination with more compatible lower weight gelatin and this balance may vary depending upon the type of micro porous inorganic components used in the ink receptive layer. Such can present manufacturing problems on scale and require strict quality control to avoid excessive cracking problems and minimize water fastness issues. Generally, a compromise is found by adding a co-binder and cross-linking the ultra low molecular weight or otherwise binding it to harden the ink receptive layer against such problems.

As indicated above, ultra low molecular weight gelatins may still require extensive cross-linking with other gelatin units or with an optional polymeric co-binder in order to avoid cracking of the media as it dries or ages. Such cross linking raises the potential problem of negating the benefits of using an ultra low molecular weight gelatin instead of longer chain gelatins, and the cross-linking with itself or presence of co-binder polymers can cause a return of the problems associated with gelatin in polymeric ink receptive coatings. Moreover, such coatings have not been successfully utilized commercially to form metallic, semi-metallic, holographic, light-emitting or luminescent images. Printing media that are based upon other acceptable aqueous polymers, such as acrylics, urethanes, polyesters, and the like are also needed.

Accordingly, there is a strong need in the art for improved light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image inkjet printable photographic media of economical cost having an improved quality control, durability and water fastness without cracking or having extended drying times.

DEFINITIONS

It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a monomelic compound" in a polymer means that more than one monomelic compound or a mixture of monomelic composition to form a hornopolymer or a mixed polymer, such as copolymer, the term copolymer may mean that two or more different types of monomelic units can be present in the composition, reference to "a binder" in a composition means that more than one film-forming binder can be present in the composition, reference to "a coating agent' includes mixtures of different coating agents, and the like.

The term "paper" or "paper substrate" with reference to the ink-jet recording medium is meant to encompass any substrate based on cellulosic fibers; synthetic polymer films and fibers such as polyamides, polyesters, polyethylene, and polyacrylic; inorganic fibers such as asbestos, ceramic, and glass fibers; and any combination of cellulosic, synthetic, and inorganic fibers or a combination of cellulosic fiber and synthetic polymer films produced by extrusion or coating the cellulosic fiber substrate. The paper or paper substrate can be composed of compressed natural or synthetic fibers, of compressed natural or synthetic solids, or of a woven appearance such as a textile or canvas. The paper or paper substrate may be an opaque or a see-through substrate such as used with an overhead projector, and the substrate may be of any dimension (e.g., size or thickness) or form (e.g., pulp, wet paper, dry paper, etc.). Also, the paper or paper substrate can have a smooth or textured appearance, e.g., a canvas-look texture. In most instances, the "paper" or "paper substrate" has been subjected to an external sizing process prior to treatment according to the methods of the invention, however sizing is not required. The paper substrate is preferably in the form of a flat or sheet structure, which structure may be of variable dimensions (e.g., size and thickness). "Paper" is meant to encompass printing paper (e.g., inkjet printing paper, etc.), writing paper, drawing paper, and the like, as well as board materials such as cardboard, poster board, Bristol board, and the like. The term "sheet" or "flat structure" is not meant to be limiting as to dimension, roughness, or configuration of the substrate useful with the present invention, but rather is meant to refer to a product suitable for coating. A sheet or flat structure can refer to a substrate having either a substantially smooth or a textured appearance, e.g., a canvas-look texture.

"Sized paper substrate" is a paper substrate as described above that has applied to its surface and/or is saturated with a sizing composition. Sizing compositions may be applied in an internal sizing step and/or in an external sizing step; preferably sizing (e.g., internal and/or external sizing) occurs prior to application of the coating composition of the invention.

"Coated paper substrate" is a paper substrate that has applied to its surface and/or is saturated with a coating composition of the invention. Coating compositions may be applied as a pre-treatment (e.g., prior to printing), simultaneously with printing, or as an after-treatment. The coating compositions of the invention are applied in quantities suitable to provide the desired characteristics, such as bleed resistance, water resistance (e.g., water-fastness) of an ink printed on coated paper substrate, etc. Multiple coatings may be applied, but one embodiment consists of a single application of the coating composition on one or both sides of a substrate to produce a high quality coated paper substrate. "Aqueous based ink" refers to an ink composed of an aqueous carrier medium (or composed of a mixed solvent medium such as a mixture of aqueous and aqueous miscible organic solvents) and a colorant, such as a dye or a pigment dispersion. An "aqueous carrier medium" is composed of water or a mixture of water and one or more water-soluble organic solvents. Exemplary aqueous based ink compositions are described in detail below. "Colorant" as used herein is meant to encompass one or more organic dyes, inorganic dyes, pigments, stains, and the like compatible for use with the polymer coatings of the invention. A colorant may be in the RGB scale, the CMY scale, or simply a white or black opaque pigment. Examples of opaque pigments are aluminas, silicas, and titanium oxide. Examples of organic pigments are micronized organic polymers that are usually not soluble in water.

The term "organic solvent" is used herein in its conventional sense to refer to a liquid organic compound, typically a monomelic organic material in the form of a liquid, preferably a relatively non-viscous liquid, the molecular structure of which contains hydrogen atoms, carbon atoms, and optionally other atoms as well, and which is capable of dissolving solids gases or liquids.

The terms "significant" or "significantly", as when used with reference to "significantly enhanced brightness" or "significantly improved water-fastness" generally refer to a difference in a quantifiable, measurable, or otherwise detectable parameter, e.g., optical density, LAB graphs (color sphere), dot spread, bleed through, between the two groups being compared (e.g., uncoated versus coated paper substrates) that is statistically significant using standard statistical tests. For example, the degree of visual wicking or water-fastness in a coated paper substrate as detected in a print assay may be quantified using standard methods, and the degree of wicking or water-fastness under different conditions can be compared for both coated and uncoated paper substrates to detect statistically significant differences. The term "predominantly", as when used with reference to the composition of a mixture of materials or a polymer, generally refers to the presence of more than 50% of the item in either a mixture or compound by percentage weight or by percentage of units, depending on the context.

The term "mainly", as when used with reference to the composition of a mixture of materials or a polymer, generally refers to the presence of more than 75% of the item in either a mixture or compound by percentage weight or by percentage of units, depending on the context.

Photograph-like quality "look and feel", when used herein refers to a printed substrate wherein the image is substantially free of the type of speckling or graininess that is usually caused by uneven absorption (or by incomplete absorption) of water soluble inks into the substrate after printing and before drying, and may be glossy, dull or semi-glossy in appearance based upon the desired result and the desired coating composition.

The terms "opaque", when used herein refer to a material that is not transparent (but may optionally have a uniform color, multiple colors, or particles of color) and images cannot be seen through it at all, or only slightly and not clearly, while the term "semi-opaque" refers to a material that is only slightly translucent such that it may have a milky appearance or show printed material in a fuzzy focus sort of way.

The term "fluid resistance" is used herein to describe the resistance of a paper substrate to penetration by a fluid, with the term "water resistance" specifically referring to resistance of a paper substrate to penetration by a fluid.

The term "water-fast," is used herein to describe a form of water resistance, and which is normally used to refer to the nature of the ink composition after drying on a substrate. In general, "water-fast" means that the dried composition is substantially insoluble in water, such that upon contact with water, the dried ink retains at least about 70%, preferably at least about 85%, and more preferably at least about 95%, of optical density.

The term "bleed resistance" is meant to refer to the retardation of the penetration of water into paper, which retardation is associated with creation of a low energy hydrophobic surface at the fiber-water interface which increases the contact angle formed between a drop of liquid and the surface, and thus decreases the wet ability. Contact angles have been shown to be sensitive to molecular packing, surface morphology, and chemical constitution of the paper substrate and any components added thereto.

The term "rub resistance" is normally meant to refer to a characteristic of the ink composition after drying on a substrate, more specifically, the ability of a printed image to remain associated with the substrate upon which it is printed despite application of force (e.g., rubbing) to the printed image. In general, "rub resistant" means that the dried ink composition is substantially resistant to rubbing force so that the dried ink retains at least about 70%, preferably at least about 85%, and more preferably at least about 95%, of optical density after rubbing of the printed image.

The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term "lower alkyl" intends an alkyl group of 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms.

The term "alkylene" as used herein refers to a difunctional, branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, including without limitation methylene, ethylene, ethane- 1,1-diyl, propane-2,2-diyl, propane-l,3-diyl, butane- 1,3-diyl, and the like. "Lower alkylene" refers to an alkylene group of 1 to 6 carbon atoms.

The terms "organic acyl", "alkanoyl", or "lower alkanoyl" or as used herein intends an alkyl group bound to a carbonyl group, and may be bonded to an imine group through the carbonyl group to form a carboxamide group. The alkyl or lower alkyl portion of the alkanoyl or lower alkanoyl, or in the generic term organic acyl, are each defined as described above for "alkyl" or "lower alkyl".

"Halo" or "halogen" refers to fluoro, chloro, bromo or iodo, and usually relates to halo substitution for a hydrogen atom in an organic compound. The term "polymer" is used herein in its conventional sense to refer to a compound having about 8 or more monomer units, and unless otherwise stated, refers to a compound having a molecular weight from about 1000 and higher. The term "oligomer" refers to a compound having from 2 to about 8 monomer units. The terms oligomer and polymer intend to cover compounds having a single type of repeating monomer unit (homopolymer or oligomer) as well as compounds containing more than one type of monomer unit (copolymers and mixed oligomers). The terms "monomer" or "monomelic" as used herein refer to compounds which are not polymeric or oligomeric as defined above.

The term "copolymer" of a monomelic component as used herein may refer to a mixed polymer having two or more types of monomelic units. When the copolymer is defined more specifically, the monomeric units are defined by percentages or predominance in the polymer.

"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase "optionally substituted" aromatic ring means that the aromatic ring may or may not be substituted and that the description includes both an unsubstituted aromatic ring and an aromatic ring bearing one or more substituents. Also, by way of example, when a component may be optionally included in a mixture it may be present or entirely absent. SUMMARY OF THE INVENTION

An object of the present invention is to provide an ink printable micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque predominantly inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image, wherein the semi-opaque or opaque layer further includes from 5% to 40% of at least one ink receptive polymer or copolymers that are cationic, charge neutral, or a combination thereof, and which include at least 50% of one or more monomer units of ethyleneimine or ethyleneimine derivatives. A particularly preferred ink receptive polymer, which is cationic, charge neutral, or a combination thereof, comprises an inkjet-receptive effective amount of a polyethylene imine derivative wherein at least 50% of the imine group are functionalized with a lower alkyl carbonyl group such as formyl, acetyl, propanoyl, isopropanoyl, butanoyl, pentanoyl, isopentanoyl, and the like to form a carboxamide group, or may be ethoxylated with treatment with epoxy such as glycidol. The amino group may optionally be further functionalized to form a quaternary ammonium group associated with an inorganic or organic anionic group. Preferably, the ink receptive polymer or copolymer is a polyethyloxazoline homopolymer from 2-ethyloxazoline or copolymer derived from at least 50% monomers of 2-ethyloxazoline. Alternatively, preferred is any cationic polyethylimine polymer or copolymer having at least 50% of their imine groups derived in the form of an acetyl carboxamide group within the polymer or copolymer.

Typically polyethyleneimine derivative polymers and copolymers are synthesized by derivatizing branched and/or linear polyethylenimine produced by homo polymerizing azirdines and its derivatives. The linear polyethyleneimine and its derivatives are preferably synthesized by homo- polymers or co-polymers produced by poly 2-ethyloxazoline by homo- polymerizing 2 ethyloxazoline monomer. 2-Polyethyloxazoline (Aquazol, ISP corp) is an example of acylated polyethyleneimine derivative which upon hydrolysis and optionally with further derivization provides linear polyethyleneimine and its derivatives. In addition to commercially available homo-polymers of 2-ethyloxazline (Aquazol, ISP Corp), the copolymers of 2 ethyloxazoline are synthesized by reacting diols, diacids, dithiols, diamines, etc. with 2-ethyloxazoline monomer.

An object of the invention is to provide such a recordable media constructed from any compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that can accept at least one layer of the semi-opaque or opaque primarily inorganic ink receptive layer coating thereon. The ink-receptive layer is composed primarily of an inorganic layer such as silica or alumina hydrate that includes an effective amount of at least one polyethylene imine derivative polymer or copolymer and one or more optional polymers and cross-linker agents. The ink-receptive layer is a topcoat layer that may be optionally coated with a porous ink-transmitting layer, wherein the porous ink-transmitting layer may be simply an ink permeable layer or contain active ingredients such as antioxidants, ultraviolet inhibitors or the like.

Another object of the invention is to provide a micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi- metallic, or metallic image including a substrate basecoat or layer that is a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image substrate base at least partially coated with the micro porous ink-receptive coating layer.

In a preferred object of the present invention, the ink-receptive layer is composed primarily of an inorganic layer such as silica, alumina hydrate or a combination thereof, preferably silica particles, alumina hydrate enriched silica particles, alumina hydrate surface- enriched particles, and mixtures thereof, wherein the inorganic layers incorporates an effective amount of at least one polyethylene imine derivative polymer or copolymer, and optionally includes one or more optional other polymers and cross-linker agents. Alumina or silica particles can be formed by fumed or precipitation processes. In some embodiments of the invention, silica or alumina can be functional ized by cationic or anionic organic or inorganic functional groups. Preferably, the ink-receptive layer is a topcoat layer for an inkjet recordable media that may be optionally further coated with another topcoat layer that is a porous ink- transmitting layer. Optional porous ink-transmitting layers also may be coated over compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layers or substrate basecoat layers prior to coating of the media with one or more ink receptive layers according to the invention.

A preferred object of the present invention is to provide such an ink-receptive layer wherein the porous inorganic components of inorganic silica or alumina hydrate are present in an amount by weight from 30% to 95%, preferably from 70% to 80%, and more preferably from 80% to 85%, and the polyethylene imine derivative polymer or copolymer is present in an amount by weight from 5% to 50%, preferably from 10% to 20% when a homo-polymeric resin is utilized and from 20% to 40% when a copolymeric resin is utilized. Preferably, the polymeric resin or co-polymeric resin has more than 50% of its imine groups present as carboxamide groups, and preferably more than 90% are present as carboxamide groups. More preferred are ink receptive layers that include from 10 to 14% of a polymeric cationic or neutral resin having at least 90% or more of the imine groups present in the form of carboxamide groups, and optionally containing from 1% to 5% of a cross-linker, preferably from 1% to 2% of such optional crosslinker or binder. Also preferred are polymeric or co- polymeric cationic resins having at least 50% or more ethyloxazoline monomeric groups that result in acetylcarboxamide groups when they are incorporated in a polymeric or copolymeric resin. Any co-monomer that is compatible with each of the monomer 2-ethyloxazoline, inorganic components and recordable inks are acceptable for forming a cationic resin for the ink receptive layer, wherein the imine groups may be optionally quaternized with any printable media compatible inorganic or organic acid. Such acceptable quaternizing agents are well known in the art. Also, optionally, cationic polyurethanes, poly-diallyl-dimethyl ammonium chloride (p-DADMAC) are added.

In one preferred object of the invention, 2-ethyloxazoline is copolymerized with one or more monomers having dithol, diol, diacids or diamine groups. Other acceptable monomers are lower cycloalkyl imines. In place of polyethyloxazoline polymers, polyalkylene imines may be modified to have amine, acid, alcohol, acyl, alkanoyl, and the like side chains.

Preferred oligomers or polymers acceptable for ink receptive agents have from 5 to 500000 monomeric units, more preferably from 5 to 300 monomeric units, and more preferably from 150 to 5000000 monomeric units. In one embodiment of the invention, homopolymers from. In general polymers in molecular weight range from 5000 to 750000 can be used alone or in combination. Poly 2-ethyloxazoline derivatives are preferred which can either be linear or branched. Another preferred such polymer is an ethoxylated polyethylene imine.

An object of the invention is to provide such ink receptive layers wherein the crosslinkers or binders compatible with the other components of the ink receptive layer are selected from polysaccharides and derivatives thereof, e.g., starches, cellulosic polymers, dextran and the like; polypeptides (e.g., collagen and gelatin); and synthetic polymers, particularly synthetic vinyl polymers such as poly(vinyl alcohol), poly(vinylpropanol), poly(vinyl phosphate), poly(vinyl pyrrolidone), vinyl-pyrrolidone-vinyl acetate copolymers, vinyl acetate-acrylic acid copolymers, vinyl alcohol-vinyl acetate copolymers, vinyl pyrrolidone-styrene copolymers, and poly( vinyl amine), synthetic acrylate polymers and copolymers such as poly(acrylic acid-co-methacrylate), poly(vinyl-co-acrylate), poly(vinylpyrrolidone-co— dimethylaminopropyl-methacrylamide), and the like, and water- soluble or water-dispersible polyesters such as sulfopolyesters (e.g., as available from Eastek). Crosslinkers or binders compatible with other components of the ink receptive layer may be cationic polyurethanes, poly-diallyl-dimethyl ammonium chloride (p-DADMAC). In a preferred object of the invention, the binder for the ink receptive layer is selected from vinyl polymers and the cross linker is selected from an azetidinium or salt cross-linker, an oxazoline derivative cross-linker, or an aziridine base or salt cross-linker.

Another object of the invention is to utilize the above ink receptive coating in combination with any compatible light-emitting, reflective, luminescent, holographic, semi- metallic or metallic base layer or substrate, preferably with an absorbent basecoat layer coated thereon prior to coating of the ink-receptive layer, to provide an ink recordable media, preferably an inkjet-receptive recordable media suitable for photographic or other graphic recording. A preferred basecoat layer includes a combination of an acceptable pigment and binder, and the basecoat may further include deformable particles, such as core-shell polymeric pigments.

A fiirther object of the invention is to provide a method for increasing the gloss, reflectivity, luminescence, metallic-looking image, or holographic-like image or surface smoothness presented by the topcoat of a printing medium by optionally including deformable particles in an underlying basecoat layer or substrate followed by calendaring of the printing medium.

A still further object of the invention is to provide a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic inkjet printing media constructed from a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that is at least partially coated with the micro porous ink-receptive coating layer.

DISCRIPTION THE INVENTION

One embodiment of the present invention provides an ink printable micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque predominantly inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image, wherein the semi-opaque or opaque layer further includes from 5% to 70% of at least one ink receptive polymer or copolymers that are cationic, neutral or a combination thereof, and which include at least 50% of one or more monomer units of ethyleneimine or ethyleneimine derivatives. A particularly preferred cationic ink receptive polymer comprises an inkjet-receptive effective amount of a polyethylene imine derivative wherein at least 50% of the imine group are functionalized with a lower alkyl carbonyl group such as formyl, acetyl, propanoyl, isopropanoyl, butanoyl, pentanoyl, isopentanoyl, and the like to form a carboxamide group, or may be ethoxylated with treatment with epoxy such as glycidol. The amino group may optionally be further functionalized to form a quaternary ammonium group associated with an inorganic or organic anionic group. Preferably, the ink receptive cationic or neutral polymer or copolymer is a polyethyloxazoline homopolymer from 2-ethyloxazoline or copolymer derived from at least 50% monomers of 2- ethyloxazoline. Alternatively, preferred is any cationic or neutral polyethylimine polymer or copolymer having at least 50% of their imine groups derived in the form of an acetyl carboxamide group within the polymer or copolymer.

Another embodiment of the invention provides an ink printable micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque predominantly inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image, wherein the semi-opaque or opaque layer further includes from 5% to 70% of at least one ink receptive polymer or copolymers that are cationic, charge neutral, or a combination thereof, and which include at least 50% of one or more monomer units of ethyleneimine or ethyleneimine derivatives. A particularly preferred ink receptive polymer, which is cationic, charge neutral, or a combination thereof, comprises an inkjet-receptive effective amount of a polyethylene imine derivative wherein at least 50% of the imine group are functionalized with a lower alkyl carbonyl group such as formyl, acetyl, propanoyl, isopropanoyl, butanoyl, pentanoyl, isopentanoyl, and the like to form a carboxamide group, or may be ethoxylated with treatment with epoxy such as glycidol. The amino group may optionally be further functionalized to form a quaternary ammonium group associated with an inorganic or organic anionic group. Preferably, the ink receptive cationic polymer or copolymer is a polyethyloxazoline homopolymer from 2-ethyloxazoline or copolymer derived from at least 50% monomers of 2-ethyloxazoline. Alternatively, preferred is any cationic polyethylimine polymer or copolymer having at least 50% of their imine groups derived in the form of an acetyl carboxamide group within the polymer or copolymer.

A further embodiment of the invention provides such a recordable media constructed from any compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that can accept at least one layer of the semi-opaque or opaque primarily inorganic ink receptive layer coating thereon. The ink-receptive layer is composed primarily of an inorganic layer such as silica or alumina hydrate that includes an effective amount of at least one polyethylene imine derivative polymer or copolymer and one or more optional cross-linker agents. The ink-receptive layer is a topcoat layer that may be optionally coated with a porous ink-transmitting layer, wherein the porous ink-transmitting layer may be simply an ink permeable layer or contain active ingredients such as anti-oxidants, ultraviolet inhibitors or the like.

Yet another embodiment of the invention provides a micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image including a substrate basecoat or layer that is a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image substrate base at least partially coated with the micro porous ink-receptive coating layer.

In a preferred embodiment, the present invention provides an ink-receptive layer composed primarily of an inorganic layer such as silica, alumina hydrate or a combination thereof, preferably silica particles, alumina hydrate enriched silica particles, alumina hydrate surface-enriched particles, and mixtures thereof, wherein the inorganic layers incorporates an effective amount of at least one polyethylene imine derivative polymer or copolymer, and optionally includes one or more optional cross-linker agents. Alumina or silica particles can be formed by fumed or precipitation processes. In some embodiments of the invention, silica or alumina can be functionalized by cationic or anionic organic or inorganic functional groups. Preferably, the ink-receptive layer is a topcoat layer for an inkjet recordable media that may be optionally further coated with another topcoat layer that is a porous ink-transmitting layer. Optional porous ink-transmitting layers also may be coated over compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layers or substrate basecoat layers prior to coating of the media with one or more ink receptive layers according to the invention.

Another preferred embodiment of the present invention provides such an ink-receptive layer wherein the porous inorganic components of inorganic silica or alumina hydrate are present in an amount by weight from 30% to 95%, preferably from 70% to 80%, and more preferably from 80% to 85%, and the polyethylene imine derivative polymer or copolymer is present in an amount by weight from 10% to 40%, preferably from 10% to 20% when a homo- polymeric resin is utilized and from 20% to 40% when a copolymeric resin is utilized. Preferably, the polymeric resin or co-polymeric resin has more than 50% of its imine groups present as carboxamide groups, and preferably more than 90% are present as carboxamide groups. More preferred are ink receptive layers that include from 10 to 14% of a polymeric cationic or neutral resin having at least 90% or more of the imine groups present in the form of carboxamide groups, and optionally containing from 1% to 5% of a cross-linker, preferably from 1% to 2% of such optional crosslinker or binder. Also preferred are polymeric or copolymeric cationic resins having at least 50% or more ethyloxazoline monomeric groups that result in acetylcarboxamide groups when they are incorporated in a polymeric or copolymeric resin. Any co-monomer that is compatible with each of the monomer 2-ethyloxazoline, inorganic components and recordable inks are acceptable for forming a cationic resin for the ink receptive layer, wherein the imine groups may be optionally quaternized with any printable media compatible inorganic or organic acid. Such acceptable quaternizing agents are well known in the art. Also, optionally, cationic polyurethanes, poly-diallyl-dimethyl ammonium chloride (p-DADMAC) are added.

In still another preferred embodiment of the invention, 2-ethyloxazoline is copolymerized with one or more monomers having dithol, diol, diacids or diamine groups. Other acceptable monomers are lower cycloalkyl imines. In place of polyethyloxazoline polymers, polyalkylene imines may be modified to have amine, acid, alcohol, acyl, alkanoyl, and the like side chains. Preferred oligomers or polymers acceptable for ink receptive agents have from 5 to 5000000monomeric units, more preferably from 5 to 300000 monomelic units, and more preferably from 150 to 250000 monomelic units. In one embodiment of the invention, homopolymers from 2-ethyloxazoline are preferred. Linear polymers having less than 25% branching are further preferred. Another preferred such polymer is an ethoxylated polyethylene imine. In general molecular weight of the polymeric binders in microporous coating is 5000 to 750000.

Yet another embodiment of the invention provides such ink receptive layers wherein the crosslinkers or binders compatible with the other components of the ink receptive layer are selected from polysaccharides and derivatives thereof, e.g., starches, cellulosic polymers, dextran and the like; polypeptides (e.g., collagen and gelatin); and synthetic polymers, particularly synthetic vinyl polymers such as poly(vinyl alcohol), poly(vinylpropanol), poly(vinyl phosphate), poly(vinyl pyrrolidone), vinyl-pyrrolidone-vinyl acetate copolymers, vinyl acetate-acrylic acid copolymers, vinyl alcohol-vinyl acetate copolymers, vinyl pyrrolidone-styrene copolymers, and poly(vinyl amine), synthetic acrylate polymers and copolymers such as poly(acrylic acid-co-methacrylate), poly(vinyl-co-acrylate), poly(vinylpyrrolidone-co— dimethylaminopropyl-methacrylamide), and the like, and water- soluble or water-dispersible polyesters such as sulfopolyesters (e.g., as available from Eastek). Crosslinkers or binders compatible with other components of the ink receptive layer may be cationic polyurethanes, poly-diallyl-dimethyl ammonium chloride (p-DADMAC) or may be ammonium zirconyl carbonate, zirconium acetate, and the like..

In one preferred embodiment of the invention, the binder for the ink receptive layer is selected from vinyl polymers and the cross linker is selected from an azetidinium or salt cross- linker, an oxazoline derivative cross-linker, or an aziridine base or salt cross-linker. Still another embodiment of the invention provides the above ink receptive coating in combination with any compatible light-emitting, reflective, luminescent, holographic, semi- metallic or metallic base layer or substrate, preferably with an absorbent basecoat layer coated thereon prior to coating of the ink-receptive layer, to provide an ink recordable media, preferably an inkjet-receptive recordable media suitable for photographic or other graphic recording. A preferred basecoat layer includes a combination of an acceptable pigment and binder, and the basecoat may further include deformable particles, such as core-shell polymeric pigments.

A further preferred embodiment of the invention provides a method for increasing the gloss, reflectivity, luminescence, metallic-looking image, or holographic-like image or surface smoothness presented by the topcoat of a printing medium by optionally including deformable particles in an underlying basecoat layer or substrate followed by calendaring of the printing medium.

A still further embodiment of the invention provides a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic inkjet printing media constructed from a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that is at least partially coated with the micro porous ink-receptive coating layer.

Another embodiment of the invention utilizes the above ink receptive coating in combination with any acceptable light-emitting, reflective, luminescent, holographic, semi- metallic or metallic base coat layer or substrate, wherein the ink receptive coating is a semi- opaque or opaque predominantly inorganic ink-receptive layer, which is rendered semi- translucent or translucent upon recording of an ink image, preferably with an absorbent basecoat layer, to provide an ink recordable media, preferably an inkjet-receptive recordable media suitable for photographic recording. A preferred basecoat layer includes a combination of an acceptable pigment and binder, and the basecoat may further include deformable particles, such as core-shell polymeric pigments.

A further embodiment of the invention provides a method for increasing the gloss, reflectivity, luminescence, metallic-looking image, or holographic-like image or surface smoothness presented by the topcoat of a printing medium by optionally including deformable particles in an underlying basecoat layer or substrate followed by calendaring of the printing medium.

A still further embodiment of the invention provides a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic inkjet printing media constructed from a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that is at least partially coated with the micro porous ink-receptive coating layer. In one embodiment, a primarily inorganic ink-receiving layer comprises up to 95% silica, alumina or a combination thereof in combination with sufficient binder to hold the particles together and may be covered with a primarily organic ink permeable ink receiving layer with up to 95% organic components, and the two layers are optimized for acceptable drying times.

The ink receptive layer may optionally include other polymer components such as up to 50% of a polymer that is soluble in an aqueous solvent or in a solvent mixture of an aqueous solvent and a polar organic solvent, and preferably up to 20% of such a polymer, wherein the polymer is a member selected from a group hydroxyethylmethacrylate copolymer or terpolymer, or a derivative thereof, and wherein the copolymer or terpolymer comprises at least one member of the group consisting of 2-hydroxyethylmethacrylate/co-acrylic acid copolymer, 2-hydroxy-ethylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/dimethyl-aminopropylmethacrylate, 2-hydroxyethylmethacrylate/dimethylaminoethybnethacrylate, and 2-hydroxyethylmethacrylatevinyl-pyrrolidone, quaternized polyhydroxyethyl-methacrylate-co- dimethylaminopropyl-methacrylate, quaternized polyhydroxyethly-methacrylate-co- dimethyl- aminoethyl-methacrylate, or a vinylpyrrolidone polymers and copolymers that are selected from the group consisting polyvinylpyrrolidone vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, vinyl caprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate terpolymer, vinylcaprolactam/vinylpyrroldone/dimethylaminopropyl methacrylamide terpolymer, vinylpyrrolidone/dimethylaminopropyl methacrylamide copolymer, vinylpyrrolidone/di-methylaminoethyl methacrylate copolymer, and quaternized derivatives thereof.

The ink receptive layer may contain an effective amount of partially or fully hydrolyzed polyvinyl alcohol and their derivatives, HEMA copolymers, vinylpyrrolidone polymers and co-polymers and cationic polyurethane and a mixture of at least two members thereof. This layer may also include an effective amount of a plasticizer which is a member selected from the group consisting of phosphates, substituted phthalic anhydrides, glycerols, and polyglycols. A preferred plasticizer is polyethylene glycol or a derivative thereof. In one embodiment, a porous layer is located above the ink receptive layer or beneath the ink receptive layer and may optionally contain pigments, optical brighteners or reflective agents. Such pigments, optical brightening agents, or reflective agents may typically be present in about 0.01 wt. % to about 20 wt% in such a porous layer, and may alternatively be present in the ink receptive layer or substrate surface when an over or under porous layer is absent. Additionally, each of the ink receptive layer or the porous under or over layer may independently further comprise organic particulates selected from the group consisting of starch, polyolefϊns, poly(methyl methacrylates), polystyrenes, polytetrafluoroethylenes, and polyurethanes, and each of the ink receptive layer, porous over or under layer, or the substrate surface upon which these layers are coated may independently further comprise additives selected from the group consisting of antifoam agents, surfactants, dyestuffs, and mixtures thereof.

The invention also provides a process of recording an image on the recording medium according to the invention, comprising the step of using a writing instrument or machine. Preferably, the writing instrument or machine is an ink-jet printer or ink-jet printing press.

Acceptable Substrates for Use in the Invention

A preferred recording medium of the invention is an ink-jet recording medium wherein the substrate is a paper or polymeric film. One preferred substrate is a paper selected from the group consisting of plain, clay-coated, resin-coated, and latex-saturated papers. Another preferred substrate is a polymeric film selected from the group consisting of polyvinyl chloride, polyethylene, polypropylene, polycarbonate, pplyimide, polyester, and fluoro-plastic films.

In one preferred embodiment of the invention, a large number of widely varying types of substrates with at least one light-emitting reflective, metallic, or luminescent surface can be utilized. Such substrates may be comprised of a material that inherently provides a light- emitting, reflective, metallic, or luminescent surface, or may be comprised of a substrate that does not have such characteristics if it can be coated or treated with a light-emitting, reflective, metallic, or luminescent material to provide the desired surface. Such substrates may be flexible or rigid, porous or nonporous, cellulosic or non-cellulosic.

Non-limiting examples of substrates suitable for use with the present invention include paper, textiles, polymeric substrates, inorganic substrates, metallic sheets, metallized polymer sheets, laminates, foil laminated polymer sheets, and the like. Specific suitable substrates examples are: polymeric films, sheets, coatings, and solid blocks, comprised of, for example, polyesters (including "MYLAR.RTM." flexible film), vinyl polymers, polysulfones, polyurethanes, polyacrylates, polyimides, or the like; metallic films, sheets, coatings, foils and solid blocks, comprised of, for example, aluminum, brass, copper, or the like; inorganic substrates in the form of films, sheets, coatings, objects, and solid blocks, comprised, of, for example, glass, metal oxides, silicon-containing ceramics, and the like; textiles having a reflective or luminescent surface; and laminates such as a paper/polymeric film, polymeric film/metal foil laminate, or paper/metal foil laminate. The nature of a substrate is not critical, but a preferred class of substrates is those having at least one light emitting, reflective, holographic, metallic, or luminescent surface that can be used in the invention to produce a reflective, holographic, light emitting, luminescent or metallic-looking image when contacted with a recording liquid in one or more steps. If a substrate that is not itself, light-emitting, reflective, holographic, metallic, or luminescent is used in the invention it may optionally be treated to provide a light-emitting, reflective, holographic, metallic, or luminescent surface. For example, a layer of a metallic foil or reflective polymeric film can be laminated to the substrate, or the substrate surface may be coated or treated with reflective or luminescent materials, for example, luminescent dyes selected from the dye families of fluorescein dyes, rhodamine dyes, pyrene dyes and porphyrin dyes.

In one embodiment of the invention, a preferred substrate comprises a paper/foil laminate or a polymer film that has been metallized by sputtering or by some other thin-layer metallizing process. The paper layer of the laminate may be formed from any convenient type of printing paper stock of desired weight, and may be in the form of a flat or sheet structure of variable dimensions. The term "paper", as used in this context, is meant to encompass printing paper (e.g., inkjet printing or conventional printing paper such as gravure, litho, etc.), writing paper, drawing paper, and the like, as well as board materials such as cardboard, poster board, Bristol board, and the like. Many such paper compositions are well known and various types of additives which can be incorporated into paper for different purposes are also well known and widely described; see for instance, Blair (ed.), The Lithographers Manual, (7th Edn.: 1983), Chapter 13, Sections 8 and 9.

Methods for preparing a paper/metal foil laminate are well-known, and well-described in the art. Also, commercial paper/foil laminates are available in a range of thicknesses and weights, such that foil papers with any desired degree of flexibility or stiffness can be selected. Those skilled in the art will be readily able to select the appropriate type of paper, foil or paper/foil laminate for use with the desired type and weight of final product to be produced. In one preferred embodiment, the inkjet recording medium comprises a substrate as described above that may be flexible or rigid, porous or nonporous, cellulosic or non-cellulosic and is coated with at least one predominantly inorganic micro porous ink receptive layer. The inkjet recording medium of the present invention may comprise a substrate wherein one or more functional or non-functional coating layers are placed between the substrate and the at least one micro porous ink receptive layer, or over the at least one micro porous ink receptive layer. Acceptable Binders for Use in the Invention

In addition to the binders mentioned above for use in the coating layers on in the substrate layers, ancillary polysaccharide binders or ancillary resin binders may be utilized. Examples of such ancillary binders are as follows.

A. Ancillary Polysaccharide Binders

Starches represent one category of suitable film-forming binders. Suitable starches may be any of a variety of natural, converted, and synthetically modified starches. Examples of such starches include: starch (e.g., SLS-280 (St. Lawrence Starch)), cationic starches (e.g., Cato-72 (National Starch), hydroxyalkylstarch, wherein the alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from about 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like (e.g., hydroxypropyl starch #02382 (PolySciences, Inc.), hydroxyethyl starch #06733 (PolySciences, Inc.), Penford Gum 270 and 280 (Penford), and Film-Kote (National Starch)), starch blends (see, e.g., U.S. Pat. No. 4,872,951 , describing a blend of cationic starch and starch treated with an alkyl or alkenyl succinic anhydride (ASA), preferably 1-octenyl succinic anhydride (OSA)), and the like. Such film-forming binder can also be synthetically produced polysaccharides, such as a cationic polysaccharide esterified by a dicarboxylic acid anhydride (see, e.g., U.S. Pat. No. 5,647,898). Additional saccharide binders include cellulosic materials such as alkyl celluloses, aryl celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkyl celluloses, dihydroxyalkyl cellulose, dihydroxyalkyl cellulose, hydroxy alkyl hydroxy alkyl cellulose, halodeoxycellulose, amino deoxycellulose, dialkylammonium halide hydroxy alkyl cellulose, hydroxyalkyl trialkyl ammonium halide hydroxyalkyl cellulose, dialkyl amino alkyl cellulose, carboxy alkyl cellulose salts, cellulose sulfate salts, carboxyalkylhydroxyalkyl cellulose and the like). Still additional film-forming binders of this type include dextran (e.g., dialkyl aminoalkyl dextran, amino dextran, and the like), carrageenan, Karaya gum, xanthan, guar and guar derivatives, (e.g., carboxyalkyl hydroxyalkyl guar, cationic guar, and the like), and gelatin.

B. Ancillary Resin Binders Additional film-forming binders are resins (e.g., such as formaldehyde resins such as melamine-formaldehyde resin, urea-formaldehyde resin, alkylated urea-formaldehyde resin, and the like), ionic polymers (e.g., poly(2-acrylamide-2 -methyl propane sulfonic acid, poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride, poly(methylene-guanidine), and the like), maleic anhydride and maleic acid-containing polymers (e.g., styrene-maleic anhydride copolymers, vinyl alkyl ether-maleic anhydride copolymers, alkylene-maleic anhydride copolymers, butadiene-maleic acid copolymers, vinylalkylether-maleic acid copolymers, alkyl vinyl ether-maleic acid esters, and the like), acrylamide-containing polymers (e.g., poly(acrylamide), acrylamide-acrylic acid copolymers, poly(N,N-dimethyl acrylamide), and the like), poly(alkylene imine)-containing polymers (e.g., poly(ethylene imine), poly(ethylene imine) epichlorohydrin, alkoxylated poly(ethylene imine), and the like), polyoxyalkylene polymers (e.g., poly(oxymethylene), poly(oxyethylene), poly(ethylene oxide), ethylene oxide/propylene oxide copolymers, ethylene oxide/2-hydroxyethyl methacrylate/ethylene oxide and ethylene oxide/hydroxypropyl methacrylate/ethyleneoxide triblock copolymers, ethylene oxide-4-vinyl pyridine/ethylene oxide triblock copolymers, ethylene oxide-isoprene/ethylene oxide triblock copolymers, epichlorohydrin-ethylene oxide copolymer, and the like), etc.

Forming Layers On The Recording Medium The compositions corresponding to micro porous ink-receptive, porous under or over layers, or basecoat layers may be applied to any acceptable light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base coat layer or substrate in any conventional manner, for example, by using a Meyer rod, slot die, roller, knife, dipping, painting, spraying, etc. Generally, coating is accomplished by dip coating, reverse roll coating, extrusion coating, or the like. If the substrate is a paper or thin polymeric film and the coating composition is applied on-machine, in order to achieve acceptable manufacture speeds of about 20 to 2000 feet per minute, preferably 20-500 feet per minute, it is recommended that the weight of the substrate, e.g., sized paper, be greater than about 30 grams per square meter. The coating compositions according to the invention can be readily prepared from commercially available starting materials and/or reagents, are compatible with additional binders or additives, can be used with a variety of substrates, are compatible with a variety of printing methods, including conventional and digital printing methods (particularly ink-jet printing, including drop-on-demand printing and continuous printing), and can also be used with existing commercial manufacturing methods and equipment, including, for example, paper production processes and equipment.

The selection of ancillary or optional ingredients for each of coating agents to create the layers described above, including the ink-receptive layer coating agent in the present coating compositions may be varied according to a variety of factors such as the nature of the substrate to be treated, the colorant to be used in printing on the treated substrate, etc. The relative ratios of ingredients within the mixture will also vary according to such factors, but typically the ratios of primary ingredients are described as above, and are varied by the inclusion of ancillary or optional ingredients to create more durable coatings for a particular substrate. In general, the pH of the ink-receptive layer coating composition is generally in the range of about 2-12, preferably at least about 2-7.5. An acidic to neutral pH is preferred when dyes or inks are neutral to basic, and a neutral to basic pH is preferred when an acidic to neutral pH dye or ink. The pH of the ink-receptive layer coating can be maintained or varied for a particular substrate by adding pH adjusters or stabilizers such as appropriate bases from ammonia, primary, secondary, and tertiary alkyl amines, ethanolamines, diamines, and the like.

Additional Components For Coating Layers

Additional components may be present in each of the coating composition utilized for ink-receptive layers or other substrate coating layers. Non-limiting examples of such additional components are inorganic fillers, anti-curl agents, surfactants, plasticizers, humectants, UV absorbers, optical brighteners, light fastness enhancers, polymeric dispersants, dye mordants and leveling agents. Such additional components and their use are commonly known in the art. Preferred additives are optical brighteners, which generally represents approximately 0.0 wt. % to 10 wt. % of a coating composition after drying on a substrate. Illustrative examples of such additives are provided in U.S. Pat. Nos. 5,279,885 and 5,537,137. The coating compositions may also include one or more crosslinking agents selected from the group consisting of zirconium acetate, ammonium zirconium carbonate, or the like, for intramolecular and/or intermolecular crosslinking of coating agents, and/or a chelating agent such as boric acid. Colorants e.g., pigments, dyes, or other colorants, may also be present in the opaque coating composition.

Preparation of the Coating Compositions

While the coating compositions can each be prepared in an organic solvent, it is preferably provided in an aqueous liquid vehicle wherein small amounts of a water-soluble organic solvent may be present. The aqueous liquid vehicle will generally be water, although other inorganic compounds which are either water-soluble or water miscible may be included as well.

On occasion it may be necessary, or desired, to add a solubilizing compound during preparation of the coating composition so that the components dissolve or disperse in the aqueous liquid vehicle, e.g., an inorganic base such as ammonia and/or an organic amine. Suitable organic amines include lower alkyl-substituted amines such as methylamine, dimethylamine, ethylamine, and trimethylamine, as well as ethanolamine, diethanolamine, triethanolamine, and substituted ethanolamines, typically lower alkyl-substituted ethanolamines such as N-methyl and N,N-dimethyl ethanolamines, and morpholine. Such compounds are also useful for bringing the pH into the desired range for basic formulations as discussed above, and, if present, will generally represent not more than about 20 wt. % of the composition, and in most cases will represent not more than about 10 wt. % of the composition.

Image Formation The recording medium according to the invention, preferably an ink-jet recording medium, is contacted with an ink or other solution to form an image on the medium. In one preferred embodiment, an image forming step is employed that involves applying an aqueous or solvent based ink to obtain desired image or background colors and thereby form a mat, glossy, or semi-glossy image. An image forming step may employ any of a variety of well- known machine or process printing techniques, such as inkjet printing, laserjet printing, flexographic printing, gravure printing and the like. In another embodiment, the image forming step may employ a writing instrument such as a pen, marker, gel pen, rollerball pen, ballpoint pen, and the like. In general, the image forming process involves applying a recording liquid in a desired image pattern to the ink-jet recording medium or other coated substrate of the invention.

Many inkjet printing processes may be utilized to form an image on the ink-jet recording medium of the invention that are well known in the art, e.g., U.S. Pat. Nos. 4,601,777; 4,251,824; 4,410,899; 4,412,224; and 4,532,530. Also, thermal ink transfer printers may be utilized, which apply an image to a substrate by a dye sublimation process, to also form mat, glossy, or semi-glossy looking images. Hot melt type inkjet printers, such as Tektronix inkjet printers that use inks formed of low melting solids are also suitable. In addition, recorded medium images can also be produced using a wide variety of other printing and imaging processes, such as offset printing, printing with pen plotters, drawing, handwriting, painting with ink pens, brush stenciling, spray painting, and the like. In one embodiment of the invention, inks are used in the formation of the image on the ink-jet recording medium or other substrates of the invention. Such an ink may be any suitable ink containing a colorant, e.g., a pigment, dye, or stain, having one or more reactive groups suitable for reacting, either covalently or ionically, with a colorant-reactive component of the opaque coating agent present on the treated substrate. Additionally, aqueous and solvent- based, dye sublimation, or hot melt inks can be utilized with the ink-jet recording medium of the invention, or other coated substrates. The particular selection of the specific ink and colorant can vary with the colorant-reactive component of the image-enhancing agent. Thus, preferred colorants for use in forming an image on a substrate treated with the present image- enhancing compositions are those containing one or more ionizable, nucleophilic or otherwise reactive moieties.

Particularly preferred colorants contained in the inks useful with the invention are thus dyes containing acidic groups (e.g., carboxylate, phosphonate, sulfonate or thiosulfonate moieties), basic groups (e.g., unsubstituted amines or amines substituted with 1 or 2 alkyl, typically lower alkyl, groups), and/or nucleophilic or otherwise reactive moieties (e.g., hydroxyl, sulfhydryl, cyano or halo). Also pigmented inks can be used as colorant. The inks can be either aqueous or solvent type.

Selection of a particular ink for recording an image upon the substrates or recording medium of the invention depends upon the requirements of a specific application, such as desired surface tension, viscosity, drying time, and the like. If an aqueous ink is selected, the aqueous liquid vehicle of inks suitable for use in the invention will generally be water, although other non-organic compounds which are either water-soluble or water miscible may be included as well. A water soluble organic vehicle such as an alcohol may also be used in such inks. The colorant may be dissolved, dispersed or suspended in the aqueous liquid (or other polar vehicle), and is present in an amount effective to provide the dried ink with the desired color and the color intensity.

As mentioned above, a can also be contained in a carrier medium composed of ink and a water-soluble organic solvent. For applications utilizing such a carrier medium, representative solvents include polyols such as polyethylene alcohol, diethylene glycol, propylene glycol, and the like. Additional solvents are simple alcohols such as ethanol, isopropanol and benzyl alcohol, and glycol ethers, e.g., ethylene glycol monomethyl ether, diethylene glycol monoethyl ether. Representative examples of water-soluble organic solvents are described in U.S. Pat. No. 5,085,698 and U.S. Pat. No. 5,441,561. Non-limiting examples of suitable water soluble organic solvents for inks that may be utilized to record an image on the recording media according to the invention, are not limited to, Ci-s-alkanols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and isobutanol; amides, e.g., dimethylformamide and dimethylacetamide; ketones and ketone alcohols, e.g., acetone and diacetone alcohol; C_2-4 -ethers, e.g. tetrahydrofuran and dioxane; alkylene glycols or thioglycols containing a C₂ -Ce alkylene group, e.g., ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol; poly(alkylene-glycol)s and poly(alkylene-thioglycol)s, e.g., diethylene glycol, thiodiglycol, polyethylene glycol and polypropylene glycol; polyols, e.g., glycerol and 1,2,6-hexanetriol; lower alkyl glycol and polyglycol ethers, e.g., 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-thanol, 2-(2-butoxyethoxy)ethanol, 3-butoxypropan-l-ol, -[2-(2- methoxyethoxy)-eth- oxy]ethanol, 2-[2-(2-ethoxyethoxy)ethoxy]-ethanol; cyclic esters and cyclic amides, e.g., optionally substituted pyrollidones; sulpholane; and mixtures containing two or more of the aforementioned water soluble organic solvents. Water insoluble organic solvents may also be used. Suitable water insoluble organic solvents include, but are not limited to, aromatic hydrocarbons, e.g., toluene, xylene, naphthalene, tetrahydronaphthalene and methyl naphthalene; chlorinated aromatic hydrocarbons, e.g., chlorobenzene, fluorobenzene, chloronaphthalene and bromonaphthalene; esters, e.g., butyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, benzyl benzoate, butyl benzoate, phenylethyl acetate, butyl lactate, benzyl lactate, diethyleneglycol dipropionate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl)phthalate; alcohols having six or more carbon atoms, e.g. hexanol, octanol, benzyl alcohol, phenyl ethanol, phenoxy ethanol, phenoxy propanol and phenoxy butanol; ethers having at least 5 carbon atoms, preferably C.sub.5-14 ethers, e.g. anisole and phenetole; nitrocellulose, cellulose ether, cellulose acetate; low odor petroleum distillates; turpentine; white spirits; naphtha; isopropylbiphenyl; terpene; vegetable oil; mineral oil; essential oil; and natural oil; and mixtures of any two or more thereof.

Specific non-limiting examples of suitable colorants are: Dispersol Blue Grains (Zeneca, Inc.), Duasyn Acid Blue (Hoechst Celanese), Duasyn Direct Turquoise Blue (Hoechst Celanese), Phthalocyanine blue (CI. 74160), Diane blue (CI. 21180), Pro-jet Cyan 1 (Zeneca, Inc.), Pro-jet Fast Cyan 2 (Zeneca, Inc.), Milori blue (an inorganic pigment equivalent to ultramarine) as cyan colorants; Dispersol Red D-B Grains (Zeneca, Inc.), Brilliant carmine 6B (CI. 15850), Pro-jet magenta 1 (Zeneca, Inc.), Pro-jet Fast magenta 2 (Zeneca, Inc.), Brilliant Red F3B-SF (Hoechst Celanese), Red 3B-SF (Hoechst Celanese), Acid Rhodamine (Hoechst Celanese), Quinacridone magenta (CI. Pigment Red 122) and Thioindigo magenta (CI. 73310) as magenta colorants; Dispersol Yellow D-7G 200 Grains (Zeneca, Inc.), Brilliant yellow (Hoechst Celanese), Pro-jet yellow 1 (Zeneca, Inc.), Pro-jet Fast Yellow 2 (Zeneca, Inc.), benzidine yellow (CI. 21090 and C.I. 21100) and Hansa Yellow (CI. 11680) as yellow colorants; organic dyes; and black materials such as carbon black, charcoal and other forms of finely divided carbon, iron oxide, zinc oxide, titanium dioxide, and the like. Specific and preferred black colorants include Acid Black 48 (Aldrich), Direct Black 58756 A (Crompton & Knowles), BPI Molecular Catalytic Gray (Brain Power), Fasday Cool Gray (Hunter Delator), Dispersol Navy XF Grains (Zeneca, Inc.), Dispersol Black CR-N Grains (Zeneca, Inc.), Dispersol Black XF Grains (Zeneca, Inc.), Disperse Black (BASF), Color Black FWI 8 (Degussa), Color Black FW200 (Degussa), Hostafine Black TS (Hoechst Celanese), Hostafme Black T (Hoechst Celanese), Duasyn Direct Black (Hoechst Celanese), Pro-jet Black 1 (Zeneca, Inc.) and Pro-jet Fast Black 2 (Zeneca, Inc.). Other suitable colorants are disclosed in U.S. Pat. Nos.4,761,180, 4,836,851, 4,994,110 and 5,098,474.

In an additional aspect of the invention light-emitting, reflective, luminescent, holographic, semi-metallic or metallic looking images can be produced by having an image or color scheme printed on the substrate prior to its being coating with one or more layers according to the invention. In such a case, images can be generated by contacting a coated substrate with an image forming or developing solution that may optionally contain a dye or colorant, as discussed above.

All patents, patent applications, journal articles and other references mentioned herein are incorporated by reference in their entireties.

Non-Limiting Examples of Embodiments

Example 1

(Single Layer) - Note: Aquazol and Poval C-506 are non-cationic

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ¹ 20

PVOH Poval C-506 (Kuraray)² 5

WS-500 (Esprix Technlogies) 3

Silica Dispersion Sylojet 4000C (Grace Davison) 40 Fumed Silica Dispersion PG-022 (Cabot Corporation) 10

Polycup 172 (an azetidinium cross linker) (Hercules Inc.) 1

Carbowax PEG 600 (Dow Chemical Company) 0.5

DiEthylene Glycol (Dow Chemicals) 0.3

BYK-348 (BYK Chemie) 0.2 IPA 10

Water 10

TOTAL 100 Parts

Example 2

(Single Layer) - Note: Witcobond @-213 is Cationic

Poly(2-ethyl-2-oxazoline), Aquazol 500 (International Specialty Products) ' 12 Polyurethane Witcobond W-213 (Chemtura, Inc.) 1.5

Silica Dispersion Sylojet 4000C (Grace Davison) 30

Silica Dispersion IJ-50 (ISP) 30 Carbowax PEG 600 (Dow Chemical Company) 0.8

DiEthylene Glycol (Dow Chemicals) 0.5

BYK-348 (BYK Chemie) 0.2

IPA _. 10

Water 15

TOTAL 100 Parts

Example 3

(Single Layer) - Note: Cartafix NTC is pDADMAC

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ^l 12

Polyurethane IJ-26 (Esprix Technologies)³ 3 Cartafix NTC (Clariant) 0.8

Silica Dispersion Sylojet 4000C (Grace Davison) 40

Fumed Silica Dispersion Cab-O-Sperse PG-022 (Cabot Corporation) 16

Carbowax PEG 600 (Dow Chemical Company) 2

Di Ethylene Glycol (Dow Chemicals) 1 BYK-348 (BYK Chemie) 0.2

IPA 10

Water 15

TOTAL 100 Parts

Example 4

(Single Layer)

Note : Polyurethane IJ-26 is cationic polyurethane Polyurethane IJ-26 (Esprix Technologies)³ 15

Polyurethane Witcobond W-213 (Chemtura, Inc.) 10

Cartafix NTC (Clariant) 2

Silica Dispersion IJ-25 (ISP) 50

Polycup 172 (Hercules Inc.) 0.8 Carbowax PEG 600 (Dow Chemical Company) 1

Di Ethylene Glycol (Dow Chemicals) 1

BYK-348 (BYK Chemie) 0.2

IPA 10

Water 10

TOTAL 100 Parts

Example 5 (Single Layer) - Note: WS-500 is an Oxazoline Cross-Linker

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ' 12

CartaCoat B930 (Clariant) 1.5

WS-500 (Esprix Technlogies) 2 Silica Dispersion IJ-50 (ISP) 22 Fumed Alumina Dispersion PG-003 (Cabot Corporation) 30

Polycup 172 (Hercules Inc.) 0.5

Carbowax PEG 600 (Dow Chemical Company) 1.8

BYK-348 (BYK Chemie) 0.2

IPA 10

TOTAL 100 Parts

Example 6 (Double Layer)

Bottom Layer:

Polyurethane IJ-26 (Esprix Technologies)³ 30

Silica Dispersion Sylojet 4000C (Grace Davison) 35

Polycup 172 (Hercules Inc.) 5

IPA 15 Water 15

TOTAL 100 Parts TOD Laver;

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ' 20

PVOH Poval C-506 (Kuraray)² 5

WS-500 (Esprix Technlogies) 3 Silica Dispersion Sylojet 4000C (Grace Davison) 40

Fumed Silica Dispersion PG-022 (Cabot Corporation) 10

Polycup 172 (Hercules Inc.) 1

Carbowax PEG 600 (Dow Chemical Company) 0.5

DiEthylene Glycol (Dow Chemicals) 0.3 BYK-348 (BYK Chemie) 0.2

IPA 10

Water 10

TOTAL 100 Parts

Example 7 (Double Layer)

Bottom Laver:

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ' 30 Polyurethane IJ-26 (Esprix Technologies)³ 30 Silica Dispersion IJ-50 (ISP) 25

Polycup 172 (Hercules Inc.) 5

IPA 10 TOTAL 100 Parts

Top Layer: Poly(2-ethyl-2-oxazoline), Aquazol 500 (International Specialty Products) ' 12

Polyurethane Witcobond W-213 (Chemtura, Inc.) 1.5

Silica Dispersion Sylojet 4000C (Grace Davison) 30

Silica Dispersion IJ-50 (ISP) 30

Carbowax PEG 600 (Dow Chemical Company) 0.8 DiEthylene Glycol (Dow Chemicals) 0.5

BYK-348 (BYK Chemie) 0.2

IPA 10

Water 15 TOTAL 100 Parts

Example 8 (Double Layer)

Bottom Layer:

Polyurethane IJ-26 (Esprix Technologies)³ 30

Witcobond W-213 (Chemtura, Inc.) 10 Silica Dispersion Sylojet 4000C (Grace Davison) 40

IPA 10

Water 10

TOTAL 100 Parts

Top Layer:

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ' 12

Polyurethane IJ-26 (Esprix Technologies)³ 3 Cartafix NTC (Clariant) 0.8

Silica Dispersion Sylojet 4000C (Grace Davison) 40

Fumed Silica Dispersion Cab-O-Sperse PG-022 (Cabot Corporation) 16

Carbowax PEG 600 (Dow Chemical Company) 2

Di Ethylene Glycol (Dow Chemicals) 1 BYK-348 (BYK Chemie) 0.2

IPA 10

Water 15

TOTAL 100 Parts Example 9 (Double Layer)

Bottom Layer:

Poly (2-ethyl-2-oxazoline) Aquazol 500 (International Speciality Products) ' 40 PVOH Poval C-506 (Kuraray)² 20

Fumed Alumina Dispersion PG-003 (Cabot) 30 IPA 5

Water 5

TOTAL 100 Parts

Top Layer:

Poly(2-ethyl-2-oxazoline) Aquazol 500 (International Specialty Products) ' 20

PVOH Poval C-506 (Kuraray)² 5

Fumed Silica Dispersion PG-022 (Cabot Corporation) 10

Polycup 172 (Hercules Inc.) 1

Carbowax PEG 600 (Dow Chemical Company) 0.5

DiEthylene Glycol (Dow Chemicals) 0.3 BYK-348 (BYK Chemie) 0.2

IPA 10

Water 10

TOTAL 100 Parts

¹ 15% by Wt. solution in water

² 15% by Wt. solution in water

³ Diluted to 7.5% by Wt. with Water

The present may be embodied in specific forms other than those particularly described above or illustrated by the appended drawings. Upon viewing the present application preferred embodiments and other descriptions herein of the present invention, variations and other implementations that do not depart from the spirit and scope of the present invention will be apparent to one of routine skill in this field. Such variations and other implementations are considered part of the present invention and within the scope of the appended claims. Accordingly, reference should be made to the appended claims, rather than to the forgoing specification and drawings, as indicating the scope of the present invention.

Claims

I CLAIM:

1 . An ink printable micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image comprising a light-emitting, reflective, luminescent, holographic, semi-metallic or metallic substrate coated with a semi-opaque or opaque predominantly inorganic ink-receptive layer that is rendered semi-translucent or translucent upon recording of an ink image, wherein the semi-opaque or opaque layer further includes from 5% to 50% of at least one ink receptive polymer or copolymers that are cationic, charge neutral, or a combination thereof, and comprise 50% of one or more monomer units of polyethyleneimine or polyethyleneimine derivatives.

2. An ink printable micro porous photo quality printable ink receiving media according to claim 1, wherein the ink receptive polymer is cationic, charge neutral, or combination thereof and comprises an inkjet-receptive effective amount of a polyethyleneimine derivative and 50% or more of the imine groups on the polyethylene imine derivitive are functional ized with a lower alkyl carbonyl group to form a carboxamide group, or may be ethoxylated with treatment with an epoxy group, and the amino group of the carboxamide may optionally be further functionalized to form a quaternary ammonium group associated with an inorganic or organic anionic group.

3. An ink printable micro porous photo quality printable ink receiving media according to claim 1, wherein the lower alkanoyl goups that functionalize 50% or more of the imine groups on the polyethylene imine derivative are selected from formyl, acetyl, propanoyl, isopropanoyl, butanoyl, pentanoyl, isopentanoyl, and the ethoxylating group is glycidol.

4. An ink printable micro porous photo quality printable ink receiving media according to claim 1, wherein the ink receptive polymer or copolymer is cationic, charge neutral, or combination thereof and is a 2-polyethyloxazoline homopolymer from 2-ethyloxazoline or copolymer derived from at least 50% monomers of 2-ethyloxazoline, or is any cationic or neutral polyethylimine polymer or copolymer having at least 50% of their imine groups derived in the form of an acetyl carboxamide group within the polymer or copolymer.

5. An ink printable micro porous photo quality printable ink receiving media, comprising a recordable media constructed from any compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layer or substrate that can accept at least one layer of the semi-opaque or opaque primarily inorganic ink receptive layer coating thereon wherein the ink-receptive layer is composed primarily of an inorganic layer such as silica, alumina hydrate or a combination thereof that includes an effective amount of at least one polyethyleneimine derivative polymer or copolymer and one or more optional cross-linker agents and the ink-receptive layer is a topcoat layer that may be optionally coated with a porous ink-transmitting layer before or after an image is recorded thereon.

6. An ink printable micro porous photo quality printable ink receiving media according to claim 5, wherein the ink receiving media is a micro porous photo quality printable ink receiving media for recording a light-emitting, reflective, luminescent, holographic, semi- metallic, or metallic image including a substrate basecoat or layer that is a light-emitting, reflective, luminescent, holographic, semi-metallic, or metallic image substrate base that is at least partially coated with the micro porous ink-receptive coating layer

7. A micro porous photo quality printable ink receiving media according to claim 6, wherein the ink-receptive layer is composed primarily of an inorganic layer such as silica or alumina hydrate, preferably silica, alumina hydrate particles, alumina hydrate enriched silica particles, alumina hydrate surface-enriched particles, and mixtures thereof, wherein the inorganic layers incorporate an effective amount of at least one polyethyleneimine derivative polymer or copolymer, and optionally include one or more optional cross-linker agents, and wherein the alumina can be formed by a fumed process, a precipitation process, or a combination thereof, and the silica or alumina particles can optionally be functional ized by cationic or anionic organic or inorganic functional groups.

8. A micro porous photo quality printable ink receiving media according to claim 7, wherein the ink-receptive layer is a topcoat layer for an inkjet recordable media that may be optionally further coated with another topcoat layer that is a porous ink-transmitting layer, and optionally may include porous ink-transmitting layers coated over compatible light-emitting, reflective, luminescent, holographic, semi-metallic or metallic base layers or substrate basecoat layers prior to coating of the media with one or more ink receptive layers.

9. A micro porous photo quality printable ink receiving media according to claim 7, comprising an ink-receptive layer wherein the porous inorganic components of inorganic silica or alumina hydrate are present in an amount by weight from 30% to 95%, and the polyethyleneimine derivative polymer or copolymer is present in an amount by weight from 5% to 70%.

10. A micro porous photo quality printable ink receiving media according to claim 9, wherein the porous inorganic components of inorganic silica or alumina hydrate are present in an amount by weight from 60% to 80%, and the polyethyleneimine derivative polymer or copolymer is present in an amount by weight from 5% to 35% when a homo-polymeric resin is utilized and from 10% to 40% when a copolymeric resin is utilized.

11. A micro porous photo quality printable ink receiving media according to claim 10, wherein the porous inorganic components of inorganic silica or alumina hydrate are present in an amount by weight from 40% to 95%.

12. A micro porous photo quality printable ink receiving media according to claim 9, wherein the homo polymeric resin or co-polymeric resin has more than 50% of its imine groups present as carboxamide groups, and preferably more than 90% are present as carboxamide groups.

13. A micro porous photo quality printable ink receiving media according to claim 12, wherein one or more of the ink receptive layers include from 5to 15% of a polymeric cationic and charge neutral resin in addition to one or more polyethyleneimine derivative polymers, and optionally containing from 0.1% to 5% of a cross-linker.

14. A micro porous photo quality printable ink receiving media according to claim 13, wherein one or more of the ink receptive layers include froml% to 10% of such optional crosslinker or binder, and the one or more polyethyleneimine derivative polymers are selected from homo- and co-polymers of 2-ethyloxazoline .

15. A micro porous photo quality printable ink receiving media according to claim 13, wherein polymeric or co-polymeric cationic resins are comprised of at least 50% of poly- ethyleneimine derivative polymers that may be converted to acetylcarboxamide groups and/or homo- or co-polymers of 2-ethyloxazoline alone or in combination with other cationic or neutral polymers as polymeric binder system of microporous coating.

16. A micro porous photo quality printable ink receiving media according to claim 15, comprising of a resin obtained by reacting any co-monomer and/or polymerization initiator that is copolymerizable with monomer 2-ethyloxazoline, and optionally further comprise inorganic components and recordable inks that are acceptable for forming a resin for the ink receptive layer that is cationic, charge neutral or a combination thereof, wherein the imine groups may be optionally quaternized with any printable media compatible inorganic or organic acid, and wherein the resin has a molecular weight from 5000 to 750000.

17. A micro porous photo quality printable ink receiving media according to claim 16, wherein 2-ethyloxazoline is copolymerized with one or more monomers having dithol, diol, diacids or diamine groups or with one or more lower cycloalkyl imines; and optionally alone or in combination with cationic organic salts, inorganic acids, organic amine salts as intitiators.

18. A micro porous photo quality printable ink receiving media according to claim 13, wherein at least one ink receptive layer comprises polyalkylene imines that may be modified to have amine, acid, alcohol, acyl, alkanoyl, and quaternary ammonium groups and the like side chains or polymer back bone, and wherein the polyalkylene imines have a molecular weight from 5000 to 750000.

19. A micro porous photo quality printable ink receiving media according to claim 13, wherein ink receptive layers comprises oligomers or polymers acceptable for ink receptive agents having a molecular weight from 5000 to 750,000, more preferably from 200,000 to 500,000, and more preferably from 250,000 to 500,000, and the basecoat layer includes a combination of an acceptable pigment and binder, wherein the basecoat may optionally further include deformable particles, such as core-shell polymeric pigments.

20. A micro porous photo quality printable ink receiving media according to claim 15, wherein homopolymers from 2-ethyloxazoline are included and are optionally linear polymers having less than 25% branching, and wherein the homopolymers have a molecular weight from 75,000 to 500,000.