Patent Description:
The following references may be relevant to the general field of technology of the present disclosure: <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT> B; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and <CIT> B. <CIT> discloses a microporous ink-receptive sheet.

Briefly, the present invention provides coatable compositions for formation of an ink receptive layer comprising a mixture of: a) colloidal silica particles having an average particle size of <NUM>-<NUM>; b) one or more polyester polymers; c) one or more polymers selected from the group consisting of polyurethane polymers and (meth)acrylate polymers; and d) one or more crosslinkers; as defined in claims <NUM> to <NUM>. For clarity, weight percentages refer to dry (solids) weight throughout unless otherwise stated. In some embodiments, the coatable composition is an aqueous suspension. In some embodiments, the one or more crosslinkers are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d). Additional embodiments of the coatable compositions of the present invention are described below under "Selected Embodiments.

In another aspect, the present invention provides ink-receptive layers comprising a mixture of: I) colloidal silica particles having an average particle size of <NUM>-<NUM>; and II) a crosslinked polymer obtained by reacting to form crosslinks a mixture of: b) one or more polyester polymers; c) one or more polymers selected from the group consisting of polyurethane polymers and (meth)acrylate polymers; and d) one or more crosslinkers; as defined in claims <NUM> to <NUM>.

For clarity, weight percentages refer to dry (solids) weight throughout unless otherwise stated. In some embodiments, the one or more polyester polymers in the ink-receptive layers include sulfonated polyester polymers. In some embodiments, the ink-receptive layers have a <NUM> degree gloss of at least <NUM>, at least <NUM>, at least <NUM>, or in some embodiments at least <NUM>. Additional embodiments of the ink-receptive layers of the present invention are described below under "Selected Embodiments.

In another aspect, the present invention provides constructions comprising the ink-receptive layer according to the present invention bound to a substrate layer comprising a material selected from the group consisting of polyester, for example polyethylene terephthalate (PET), polypropylene (PP), vinyl and polyvinyl chloride (PVC). Additional embodiments of the constructions of the present invention are described below under "Selected Embodiments.

The preceding summary of the present invention is not intended to describe each embodiment of the present invention. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.

As used herein, "have", "having", "include", "including", "comprise", "comprising" or the like are used in their open ended sense, and generally mean "including, but not limited to. " It will be understood that the terms "consisting of" and "consisting essentially of" are subsumed in the term "comprising," and the like.

The present invention provides printable durable labels and components thereof, including ink-receptive layers, as well as coatable compositions such as may be used to make such ink-receptive layers.

The coatable compositions and ink-receptive layers contain small-diameter colloidal silica particles. Despite the silica particle content, the ink-receptive layers display high gloss, yet they also possess high affinity for printable inks. In addition, high scratch and smear resistance was also observed.

The coatable compositions of the present invention are typically aqueous suspensions. In some embodiments, all constituents of the suspension other than water or solvents are in suspension. In some embodiments, some constituents of the suspension are in suspension and some are partly or fully dissolved. In some embodiments, the suspension is in water without additional solvents. In some embodiments, the suspension is in water and additional water-miscible solvents. In some embodiments, the suspension is in water and additional water-soluble solvents. The coatable composition of the present invention may optionally include a coalescing agent. Any suitable coalescing agent may be used in the practice of the present disclosure. In some embodiments, the coalescing agent may be one or more of N-methylpyrrolidone (NMP) or di(propylene glycol) methyl ether (DPGME). In some embodiments, the suspension has a pH of <NUM>-<NUM>, in some <NUM>-<NUM>, and in some <NUM>-<NUM>.

The coatable composition of the present invention may be made by any suitable means. Typically, the coatable composition of the present invention may be made by mixing of its components. In some embodiments, the coatable composition of the present invention is maintained at a high pH during mixing, in some embodiments at a pH of <NUM>-<NUM>, in some <NUM>-<NUM>, and in some <NUM>-<NUM>.

Any suitable colloidal silica may be used in the practice of the present invention. Colloidal silica is a form of silicon dioxide having an amorphous structure, distinguished from crystalline forms of silicon dioxide. Colloidal silica may comprise approximately spherical particles. Colloidal silica may comprise particles having an average diameter of <NUM> to <NUM> nanometers. Colloidal silica may be maintained in a largely unaggregated and unagglomerated form, typically in aqueous suspension at basic pH or slightly acidic. Colloidal silica is distinguished from non-colloidal silica such as fumed silica and silica gels, which comprise aggregated, agglomerated, or fused silica particles. Colloidal silica used in the practice of the present invention has an average particle diameter of <NUM> to <NUM> nanometers, in some such embodiments greater than <NUM> nanometers, in some greater than <NUM> nanometers, in some greater than <NUM> nanometers, in some greater than <NUM> nanometers, in some greater than <NUM> nanometers, in some greater than <NUM> nanometers, and in some greater than <NUM> nanometers. In some such embodiments, average silica particle diameter is less than <NUM> nanometers, in some less than <NUM> nanometers, in some less than <NUM> nanometers, in some less than <NUM> nanometers, in some less than <NUM> nanometers, and in some such embodiments less than <NUM> nanometers. In some embodiments, the silica particles are monodisperse, where <NUM>% or more of the particles fall within +/-<NUM>, +/-<NUM>, or +/-<NUM> of the average particle diameter. In some embodiments the silica particles are not surface-modified. In some embodiments the silica particles are not surface-modified by attachment of organic molecules to the particle surface. In some embodiments the silica particles are not surface-modified by covalent attachment of organic molecules to the particle surface. In some embodiments the silica particles are not surface-modified by ionic attachment of organic molecules to the particle surface. In some embodiments, the silica particles comprise hydroxy groups (e.g., in the form of silanol groups) on the particle surface.

Any suitable polyester polymers may be used in the practice of the present invention. In some embodiments, suitable polyester polymers are sulfonated. In some embodiments, suitable polyester polymers are not sulfonated. Suitable sulfonated and non-sulfonated polyester polymers may include those described in <CIT>.

In some embodiments, suitable polyester polymers are copolyesters. In some embodiments, suitable polyester polymers are polyester-polyether copolyesters. In some embodiments, suitable polyester polymers are grafted with additional polymeric material. In some embodiments, suitable polyester polymers are not grafted with additional polymeric material. In some embodiments, suitable polyester polymers are branched. In some embodiments, suitable polyester polymers are not branched. In some embodiments, suitable polyester polymers are carboxyl-terminated. In some embodiments, suitable polyester polymers are hydroxy-terminated. In some embodiments, suitable polyester polymers comprise not more than <NUM> weight percent of monomer units derived from monomers other than polyacid or polyol monomers, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, and in some embodiments not more than <NUM> weight percent.

Any suitable polyurethane polymers may be used in the practice of the present invention. In some embodiments, suitable polyurethane polymers have an aliphatic backbone structure. In some embodiments, suitable polyurethane polymers are nonaromatic. In some embodiments, suitable polyurethane polymers are grafted with additional polymeric material. In some embodiments, suitable polyurethane polymers are not grafted with additional polymeric material. In some embodiments, suitable polyurethane polymers are branched. In some embodiments, suitable polyurethane polymers are not branched. In some embodiments, suitable polyurethane polymers are carboxyl-terminated. In some embodiments, suitable polyurethane polymers comprise not more than <NUM> weight percent of monomer units derived from monomers other than polyisocyanate or polyols monomers, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, and in some embodiments not more than <NUM> weight percent.

Any suitable (meth)acrylate polymers may be used in the practice of the present invention. In some embodiments, suitable (meth)acrylate polymers are in the form of a core-shell particles in a latex. Suitable (meth)acrylate polymers, including core-shell (meth)acrylate polymers, may include those described in <CIT>.

In some embodiments, suitable (meth)acrylate polymers are grafted with additional polymeric material. In some embodiments, suitable (meth)acrylate polymers are not grafted with additional polymeric material. In some embodiments, suitable (meth)acrylate polymers are branched. In some embodiments, suitable (meth)acrylate polymers are not branched. In some embodiments, suitable (meth)acrylate polymers comprise not more than <NUM> weight percent of monomer units derived from monomers other than (meth)acrylate monomers, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, in some not more than <NUM> weight percent, and in some embodiments not more than <NUM> weight percent.

Any suitable crosslinkers may be used in the practice of the present invention. In some embodiments, suitable crosslinkers are reactive with polyesters. In some embodiments, suitable crosslinkers are reactive with polyesters and polyurethanes. In some embodiments, suitable crosslinkers are reactive with polyesters and (meth)acrylates. In some embodiments, the crosslinkers are selected from polyaziridines comprising two or more aziridine groups. In some embodiments, the crosslinkers are selected from carbodiimide crosslinkers. In some embodiments, the crosslinkers are selected from isocyanate crosslinkers. In some embodiments, the crosslinkers are selected from silane crosslinkers. In some embodiments, the crosslinkers are selected from metal complex crosslinkers. In some embodiments, the crosslinkers are selected from UV-activated crosslinking systems. In some embodiments, the crosslinkers do not include UV-activated crosslinking systems. In some embodiments, the crosslinkers are heat-activated crosslinking systems.

Ink-receptive layers according to the present invention may be made by any suitable means. In some embodiments, ink-receptive layers according to the present invention ; are made by coating out the coatable composition of the present invention. Coating may be accomplished by any suitable means, which may include spraying, bar coating, dipping, brushing, curtain coating, roll coating, gravure coating, screen printing, and the like. In some embodiments, coating is performed on a substrate. In some embodiments, coating step(s) may be followed by drying steps. In some embodiments, coating step(s) may be followed by steps promoting reaction of crosslinker(s), if present, with polymers. In some embodiments, drying steps and steps promoting reaction of crosslinker(s) are carried out simultaneously, e.g., by application of heat. In some embodiments, steps promoting reaction of crosslinker(s) are carried out by application of UV radiation.

Any suitable substrates may be used in the practice of the present invention. In some embodiments, the substrate may comprise one or more of polyester, for example polyethylene terephthalate (PET), polypropylene (PP), vinyl, polyolefins or polyvinyl chloride (PVC). In some embodiments, additional layers may be added to the substrate. In some embodiments, such additional layers may include adhesive layers. In some embodiments, the substrate bears an adhesive layer on the face opposite the face bearing the ink-receptive layer. In some such embodiments, the adhesive is a pressure sensitive adhesive (PSA). In some embodiments including an adhesive layer, the adhesive layer is covered with a liner.

In some embodiments, the ink-receptive layer of the present invention readily anchors one, more, or many inks types, which may include one or more of: water-based inks, organic solvent-based inks, and UV curable inks. In some embodiments, the ink-receptive layer of the present invention may be readily used with one, more, or many printing technologies, which may include one or more of: flexographic, ink jet, and thermal transfer technologies.

In some embodiments, the ink-receptive layers may exhibit an unusual microporous structure due to the inclusion of fine colloidal silica. Without wishing to be bound by theory, applicants believe that such a structure may play a role in the ability of the ink-receptive layers of the present invention to simultaneously achieve conflicting goals: high gloss, high affinity for printable inks, and high durability (e.g., high scratch and smear resistance).

In some embodiments, the ink-receptive layers exhibit unusual surface smoothness. In some embodiments, surface smoothness (i.e., lack of roughness) may be measured by atomic force microscopy (AFM). In some embodiments, the ink-receptive layers exhibit surface smoothness to the extent that Ra is less than <NUM>, in some embodiments less than <NUM>, in some embodiments less than <NUM>, and in some embodiments less than <NUM>, despite inclusion of colloidal silica particles. In some embodiments, the ink-receptive layers exhibit surface smoothness to the extent that Rq is less than <NUM>, in some embodiments less than <NUM>, in some embodiments less than <NUM>, and in some embodiments less than <NUM>, despite inclusion of colloidal silica particles.

Additional embodiments may include those limited to the compositions or ranges recited in the Selected Embodiments below.

The present invention according to claim <NUM> is directed to a coatable composition for formation of an ink-receptive layer selected from coatable composition A or coatable composition B.

In a first embodiment thereof the inventive coatable composition is coatable composition A which comprises a mixture of:.

The second embodiment is the coatable composition A according to the first embodiment, which is an aqueous suspension.

The third embodiment is the coatable composition A according to any of the previous embodiments wherein the colloidal silica particles are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The fourth embodiment is the coatable composition A according to any of the previous embodiments wherein the colloidal silica particles are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The fifth embodiment is the composition A according to any of the previous embodiments wherein the colloidal silica particles have an average particle size of at least <NUM> or at least <NUM>.

The sixth embodiment is the coatable composition A according to any of the previous embodiments wherein the colloidal silica particles have an average particle size of not more than <NUM> or not more than <NUM> or not more than <NUM> or not more than <NUM>.

The seventh embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more polyester polymers are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The eighth embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more polyester polymers are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The ninth embodiment is the coatable composition A according to any of the previous embodiments wherein c) is present in an amount of <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The tenth embodiment is the coatable composition A according to any of the previous embodiments wherein c) is present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The eleventh embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more crosslinkers are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The twelfth embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more crosslinkers are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The thirteenth embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more polyester polymers include sulfonated polyester polymers or wherein the one or more polyester polymers are sulfonated polyester polymers.

The fourteenth embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more polyester polymers include non-sulfonated polyester polymers or wherein the one or more polyester polymers are non-sulfonated polyester polymers. The fifteenth embodiment is the coatable composition A according to any of the previous embodiments wherein c) includes one or more polyurethane polymers or wherein c) is one or more polyurethane polymers.

The sixteenth embodiment is the coatable composition A according to any of the previous embodiments wherein c) includes one or more polyurethane polymers having an aliphatic backbone or wherein c) is one or more polyurethane polymers having an aliphatic backbone.

The seventeenth embodiment is the coatable composition A according to any of the previous embodiments wherein c) includes one or more (meth)acrylate polymers or wherein c) is one or more (meth)acrylate polymers.

The eighteenth embodiment is the coatable composition A according to any of the previous embodiments wherein c) includes one or more (meth)acrylate polymers in the form of core-shell particles or wherein c) is one or more (meth)acrylate polymers in the form of core-shell particles.

The nineteenth embodiment is the coatable composition A according to any of the previous embodiments wherein the one or more crosslinkers include one or more polyaziridines or wherein the one or more crosslinkers are one or more polyaziridines.

The following embodiments are directed to inventive coatable composition B.

In the twentieth embodiment the inventive coatable composition is coatable composition B which comprises a mixture of:.

The twenty-first embodiment is the coatable composition B according to the twentieth embodiment, which is an aqueous suspension.

The twenty-second embodiment is the coatable composition B according to the previous embodiments, wherein the colloidal silica particles are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d).

The twenty-third embodiment is the coatable composition B according to the previous embodiments, wherein the colloidal silica particles are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The twenty-fourth embodiment is the coatable composition B according to the previous embodiments, wherein the colloidal silica particles have an average particle size of at least <NUM> or at least <NUM><NUM>.

The twenty-fifth embodiment is the coatable composition B according to the previous embodiments, wherein the colloidal silica particles have an average particle size of not more than <NUM> or not more than <NUM> or not more than <NUM> or not more than <NUM>.

The twenty-sixth embodiment is the coatable composition B according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The twenty-seventh embodiment is the coatable composition B according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The twenty-eighth embodiment is the coatable composition B according to the previous embodiments, wherein c) is present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The twenty-ninth embodiment is the coatable composition B according to the previous embodiments, wherein c) is present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The thirtieth embodiment is the coatable composition B according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of at least <NUM> wt%, based on the total weight of a), b), c), and d) or at least <NUM> wt%, based on the total weight of a), b), c), and d).

The thirty-first embodiment is the coatable composition B according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of not more than <NUM> wt%, based on the total weight of a), b), c), and d) or not more than <NUM> wt%, based on the total weight of a), b), c), and d).

The thirty-second embodiment is the coatable composition B according to the previous embodiments, wherein the one or more polyester polymers include sulfonated polyester polymers or wherein the one or more polyester polymers are sulfonated polyester polymers.

The thirty-third embodiment is the coatable composition B according to the previous embodiments, wherein the one or more polyester polymers include non-sulfonated polyester polymers or the one or more polyester polymers are non-sulfonated polyester polymers.

The thirty-fourth embodiment is the coatable composition B according to the previous embodiments, wherein c) includes one or more polyurethane polymers or wherein c) is one or more polyurethane polymers.

The thirty-fifth embodiment is the coatable composition B according to the previous embodiments, wherein c) includes one or more polyurethane polymers having an aliphatic backbone or wherein c) is one or more polyurethane polymers having an aliphatic backbone.

The thirty-sixth embodiment is the coatable composition B according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers or wherein c) is one or more (meth)acrylate polymers.

The thirty-seventh embodiment is the coatable composition B according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers in the form of core-shell particles or wherein c) is one or more (meth) acrylate polymers in the form of core-shell particles.

The thirty-eighth embodiment is the coatable composition B according to the previous embodiments, wherein the one or more crosslinkers include one or more polyaziridines or wherein.

the one or more crosslinkers are one or more polyaziridines. The present invention according to claim <NUM> is directed to an ink-receptive layer selected from ink-receptive layer C or ink-receptive layer D.

In the thirty-ninth embodiment the inventive ink-receptive layer is ink-receptive layer C which comprises a mixture of:.

The fortieth embodiment is the ink-receptive layer C according to the thirty-ninth embodiment, wherein the colloidal silica particles are present in an amount of at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The forty-first embodiment is the ink-receptive layer C according to the previous embodiments, wherein the colloidal silica particles are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The forty-second embodiment is the ink-receptive layer C according to the previous embodiments, wherein the colloidal silica particles have an average particle size of at least <NUM> or at least <NUM>.

The forty-third embodiment is the ink-receptive layer C according to the previous embodiments, wherein the colloidal silica particles have an average particle size of not more than <NUM> or not more than <NUM> or not more than <NUM> or not more than <NUM>.

The forty-fourth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The forty-fifth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The forty-sixth embodiment is the ink-receptive layer C according to the previous embodiments, wherein
c) is present in an amount of <NUM> wt%, based on the total weight of I), b), c), and d) or.

The forty-seventh embodiment is the ink-receptive layer C according to the previous embodiments, wherein
c) is present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or.

The forty-eighth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The forty-ninth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The fiftieth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more polyester polymers include sulfonated polyester polymers or wherein the one or more polyester polymers are sulfonated polyester polymers.

The fifty-first embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more polyester polymers include non-sulfonated polyester polymers or wherein the one or more polyester polymers are non-sulfonated polyester polymers.

The fifty-second embodiment is the ink-receptive layer C according to the previous embodiments, wherein c) includes one or more polyurethane polymers or wherein c) is one or more polyurethanes.

The fifty-third embodiment is the ink-receptive layer C according to the previous embodiments, wherein c) includes one or more polyurethane polymers having an aliphatic backbone or wherein c) is one or more polyurethane polymers having an aliphatic backbone.

The fifty-fourth embodiment is the ink-receptive layer C according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers or wherein c) is one or more (meth)acrylate polymers.

The fifty-fifth embodiment is the ink-receptive layer C according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers in the form of core-shell particles or wherein c) is one or more (meth)acrylate polymers in the form of core-shell particles.

The fifty-sixth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the one or more crosslinkers include one or more polyaziridines or wherein the one or more crosslinkers are one or more polyaziridines.

The fifty-seventh embodiment is the ink-receptive layer C according to the previous embodiments, which has a <NUM> degree gloss of at least <NUM> or a <NUM> degree gloss of at least <NUM> or a <NUM> degree gloss of at least <NUM> or a <NUM> degree gloss of at least <NUM>.

The fifty-eighth embodiment is the ink-receptive layer C according to the previous embodiments, which includes pores having a diameter of <NUM> micrometers or greater, and wherein such pores are present in a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers.

The fifty-ninth embodiment is the ink-receptive layer C according to the previous embodiments, which includes pores having a diameter of <NUM>. <NUM> micrometers or greater, and wherein such pores are present in a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers.

The sixtieth embodiment is the ink-receptive layer C according to the previous embodiments, wherein the pores have an average pore size of not more than <NUM> micrometers or not more than <NUM> micrometers.

The sixty-first embodiment is the ink-receptive layer C according to the previous embodiments, wherein the pores are non-syntactic.

The following embodiments are directed to ink-receptive layer D.

In the sixty-second embodiment the inventive ink-receptive layer is ink-receptive layer D which comprises a mixture of:.

The sixty-third embodiment is the ink-receptive layer D according to the sixty-second embodiment, wherein the colloidal silica particles are present in an amount of at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The sixty-fourth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the colloidal silica particles are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The sixty-fifth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the colloidal silica particles have an average particle size of at least <NUM>. or at least <NUM>.

The sixty-sixth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the colloidal silica particles have an average particle size of not more than <NUM> or not more than <NUM> or not more than <NUM> or not more than <NUM>.

The sixty-seventh embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of at least <NUM> wt%, based on the total weight of I), b), c) and d) or at least <NUM> wt%, based on the total weight of I), b), c) and d).

The sixty-eighth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more polyester polymers are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The sixty-ninth embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) is present in an amount of at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The seventieth embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) is present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b), c), and d).

The seventy-first embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of at least <NUM> wt%, based on the total weight of I) b), c), and d) or at least <NUM> wt%, based on the total weight of I), b), c), and d).

The seventy-second embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more crosslinkers are present in an amount of not more than <NUM> wt%, based on the total weight of I), b), c), and d) or not more than <NUM> wt%, based on the total weight of I), b) c), and d).

The seventy-third embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more polyester polymers include sulfonated polyester polymers or wherein the one or more polyester polymers are sulfonated polyester polymers.

The seventy-fourth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more polyester polymers include non-sulfonated polyester polymers or wherein the one or more polyester polymers are non-sulfonated polyester polymers.

The seventy-fifth embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) includes one or more polyurethane polymers or wherein c) is one or more polyurethane polymers.

The seventy-sixth embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) includes one or more polyurethane polymers having an aliphatic backbone or wherein c) is one or more polyurethane polymers having an aliphatic backbone.

The seventy-seventh embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers or wherein c) is one or more (meth)acrylate polymers.

The seventy-eighth embodiment is the ink-receptive layer D according to the previous embodiments, wherein c) includes one or more (meth)acrylate polymers in the form of core-shell particles or wherein c) is one or more (meth)acrylate polymers in the form of core-shell particles.

The seventy-ninth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the one or more crosslinkers include one or more polyaziridines or wherein the one or more crosslinkers are one or more polyaziridines.

The eightieth embodiment is the ink-receptive layer D according to the previous embodiments, having a.

The eighty-first embodiment is the ink-receptive layer D according to the previous embodiments, which includes pores having a diameter of <NUM> micrometers or greater, and wherein such pores are present in a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers.

The eighty-second embodiment is the ink-receptive layer D according to the previous embodiments, which includes pores having a diameter of <NUM> micrometers or greater, and wherein such pores are present in a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers or a density such that a cross-section of the ink-receptive layer intersects <NUM> or more of such pores per <NUM> square micrometers.

The eighty-third embodiment is the ink-receptive layer D according to the previous embodiments, wherein the pores have an average pore size of not more than <NUM> micrometers or not more than <NUM> micrometers.

The eighty-fourth embodiment is the ink-receptive layer D according to the previous embodiments, wherein the pores are non-syntactic.

The present invention according to claim <NUM> is directed to construction.

The eighty-fifth embodiment is a construction comprising the ink-receptive layer according to any of embodiments thirty-nine to eighty-four above bound to a substrate layer comprising a material selected from the group consisting of polyester, polyethylene terephthalate (PET), polypropylene (PP), vinyl and polyvinyl chloride (PVC).

The eighty-sixth embodiment is the construction of embodiment eighty-five wherein the ink-receptive layer is directly adjacent to and directly bound to the substrate layer.

The eighty-seventh embodiment is the construction according to the previous construction embodiments which additionally comprises a layer of pressure sensitive adhesive bound to the substrate layer.

The eighty-eighth embodiment is the construction according to embodiment eighty-seven wherein the layer of pressure sensitive adhesive is directly adjacent to and directly bound to the substrate layer.

Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure, but the scope of the invention is defined by the appended claims.

Unless otherwise noted, all reagents were obtained or are available from Aldrich Chemical Co. , Milwaukee, WI, or from other commercial chemical suppliers or may be synthesized by known methods. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, unless noted otherwise. The following abbreviations are used: m =meters; cm = centimeters; mm = millimeters; µm = micrometers; ft = feet; in = inch; RPM = revolutions per minute; kg = kilograms; oz = ounces; lb = pounds; Pa = Pascals; sec = seconds; min = minutes; and hr = hours. The terms "weight %", "% by weight", and "wt%" are used interchangeably.

Aqueous coating formulations listed in Tables <NUM>-<NUM> below were prepared by sequentially combining silica components (if present), acrylate components (if present), polyester components, polyurethane components (if present), foam control agents (if present), and crosslinkers, with gentle shaking/stirring (~<NUM> seconds) after addition of each component.

Coating Formulations described in Tables <NUM>-<NUM> were coated onto untreated <NUM> mil (<NUM>) white polyester (PET) substrates (<NUM>, Greenville, SC) using a #<NUM> Mayer rod (available from RD Specialties, Inc. , Webster, NY). The coated samples were heated to <NUM>°F for <NUM> see to effect drying. Unless otherwise indicated, coated samples employing PET substrates were used for printing and testing.

The gloss of coated samples was measured using a micro-TRI-gloss meter (a portable glossmeter available from BYK-Gardner USA, Columbia MD), which simultaneously measured gloss at <NUM>, <NUM>, and <NUM> degrees. Unless otherwise noted, three gloss measurements from three different locations from each coated sample were taken, and the gloss value results averaged. The averaged results are reported for the <NUM> degree measurement and are presented in Table <NUM>, below.

The results in the above table show that the inventive coating formulations maintain high gloss, even with high loadings of <NUM> nanometer diameter silica particles. On the other hand, Comparative Example CE-<NUM>, which included fumed silica, displayed low gloss.

Anchorage of coatings to PET substrates was evaluated in the following manner. Coated PET samples having dimensions of at least <NUM> inches x <NUM> inches (<NUM> x <NUM>) were secured onto flat, non-abrasive surfaces with strong-tack adhesive tape (available from <NUM> Company under the trade designation <NUM> Filament tape No. <NUM>). The coated PET sample was scored using a cross hatch cutter with the blade spacing of <NUM> (available from BYK-Gardner USA, Columbia MD) diagonally from top left to bottom right and then top right to bottom left which created scored array of diamond patterns. Mild force was applied while scoring the sample. A <NUM> inch x <NUM> inches (<NUM> x <NUM>) strip of high-performance, transparent cellophane film tape (available from <NUM> Company under the trade designation Scotch Cellophane Film Tape <NUM>) was laminated over the scored sample. Moderate thumb pressure was applied to the laminated area. A fine point permanent marker was used to mark the outer borders of the laminated filament tape to delineate two one-square-inch areas. The left square inch area was labeled "Slow Peel". The right square inch area was labeled "Fast Peel". The cellophane tape was peeled at approximately <NUM> in/min rate and at <NUM> degree peel angle for Slow Peel area. Once slow peeling approached the Fast Peel area, the cellophane tape was peeled at approximately <NUM> in/min rate and at <NUM> degree peel angle. Percent coating remaining was analyzed by observing loss of coating from the PET substrate, and percent (%) coating remaining was reported. Table <NUM> shows results of coating anchorage to PET substrate, for coatings derived from various coating formulations.

The ink receptivity of the coated samples (PET substrates) by flexographic and UV inkjet printing was evaluated as follows.

Coated samples were cut to approximately <NUM> inches × <NUM> inches (<NUM> × <NUM>). A hand ink proofer (available from Pamarco, Inc. , Roselle, NJ) was cleaned thoroughly with water and dried. Coated samples were secured to a flat surface using filament tape, with the longer dimension running down-web. A disposable pipette was used to draw water-borne black ink (available from Siegwerk Environmental Inks, Morganton, NC), and was dispensed between the anilox and stainless steel cylinder of the hand ink proofer. To ensure good ink distribution, the ink-loaded hand ink proofer was rolled back and forth within a small distance at the top of the coated sample, where the printing was to begin. Ink was then applied with single draw, going from the top to the bottom of the coated sample. The ink-coated sample was inspected for uniformity and defects. The ink-coated sample was allowed to dry for a few minutes under ambient conditions before further testing.

Coated samples were cut to approximately <NUM> inches × <NUM> inches (<NUM> × <NUM>) dimensions, were affixed to a slide table transport mechanism <NUM> ft/min (<NUM>/s), and were printed with cyan, magenta, and black inks in various patterns (color blocks, color barcodes, <NUM>-D barcodes, and color letters) using a Prototype & Production Systems, Inc. DICElab process development printer equipped with Fujifilm StarFire SG1024 print heads using PPSI DICEjet Gamma ink (<NUM> dpi × <NUM> dpi resolution), and cured inline using an Omnicure AC475-<NUM> UV LED lamp.

Anchorage of the ink (either flexographically printed with the hand ink proofer or UV printed) to the coatings of the coated samples was evaluated in the same fashion as the Coating Anchorage Testing as previously described, but printed samples (from either flexographic or UV inkjet printing) were used rather than unprinted samples. Percent ink remaining was analyzed by observing loss of ink from the coating of the coated sample, and percent (%) ink remaining was reported.

UV inkjet print quality on coated samples was assessed qualitatively on a <NUM> to <NUM> scale based on: resolution of the print, sharpness, and observable quality of fonts, numbers, and images. A print quality rating of <NUM> indicates a perfect (or nearly perfect) observable print with excellent resolution and image quality. In contrast, a print quality rating of <NUM> means poor observable print, which includes ink smearing and signs of streaking.

Flexographic print scratch resistance on coated samples was qualitatively assessed on a <NUM> to <NUM> scale by scratching the printed surface with the thumbnail and assessing the result. A scratch resistance rating of <NUM> indicates excellent resistance to thumb nail abrasion, whereas a rating of <NUM> indicates complete removal of ink upon thumb nail abrasion.

Flexographic print smear resistance on coated was qualitatively assessed on a <NUM> to <NUM> scale by smearing the printed surface with thumb pressure and assessing the result. A smear resistance rating <NUM> indicates that the sample showed excellent (e.g., complete) resistance to ink smearing, and rating <NUM> indicates a complete removal of ink upon smearing.

Additional print assessment tests were done for Coating Formulation EX-<NUM> coated on to different film substrates - polypropylene (PP) and polyvinyl chloride (PVC). Treated PP film (<NUM> thickness) was obtained from Jindal Films America LLC (LaGrange, GA) and used as received. PVC film (<NUM> thickness) was obtained from Mississippi Polymers (Corinth, MS) and pretreated using SSA EXTENDERS OVERPRINT* <NUM># chemical (Flint Group Narrow Web, Anniston, AL) prior to coating. Coating Formulation EX-<NUM> was coated onto Treated PP film and Treated PVC film substrates using Mayer Rod Coating in the same manner as previously described for PET substrates. Flexographic and UV inkjet printing onto the Treated PP and Treated PVC coated substrates were evaluated in the same fashion as previously described for PET coated substrates. The results are shown in Tables <NUM>-<NUM>.

Claim 1:
A coatable composition for formation of an ink-receptive layer selected from coatable composition A or coatable composition B, where coatable composition A comprises a mixture of:
a) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of colloidal silica particles having an average particle size of <NUM>-<NUM>;
b) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more polyester polymers;
c) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more polymers selected from the group consisting of polyurethane polymers and (meth)acrylate polymers; and
d) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more crosslinkers;
and coatable composition B comprises a mixture of:
a) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of colloidal silica particles having an average particle size of <NUM>-<NUM>;
b) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more polyester polymers;
c) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more polymers selected from the group consisting of polyurethane polymers and (meth)acrylate polymers; and
d) <NUM>-<NUM> wt%, based on the total weight of a), b), c), and d), of one or more crosslinkers.