Ink jet recording media having a coating comprising alumina...

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Reexamination Certificate

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Reexamination Certificate

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06565949

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to coated ink jet recording media suitable for use in making film laminates and film laminates thereof. The ink jet recording media are coated with compositions comprising alumina hydrate particulate and are capable of providing recorded images having good image quality, waterfastness, and lightfastness.
2. Brief Description of the Related Art
In recent years, large format ink jet printers have been used to manufacture large color-printed media, such as graphic art indoor and outdoor advertising displays. The large format ink jet printers impart high loadings of ink onto an ink jet recording medium having an ink-receptive coating on its surface.
Since large-format printed media are often displayed indoors or outdoors, the printed medium should possess good water-resistance, smear-resistance and image quality. Most ink jet recording media are coated papers or coated polymeric films, and the ink-receptive coatings thereon usually contain water-soluble or water-swellable polymers. Thus, recorded images on these ink-jet recording media usually have poor water-resistance and smear-resistance. Previous attempts have been made at developing ink jet media to provide recorded images with good image quality, waterfastness, and lightfastness.
For example, Cousin et al., U.S. Pat. 4,554,181 describes coating an ink jet recording sheet with a coating comprising a cationic polymer and a water-soluble polyvalent metal salt to improve image quality, waterfastness, and feathering. Representative cationic polymers are described as homopolymers or copolymers of cationic monomers such as quaternary diallyldialkylammonium chlorides. The coating composition may also comprise a water-swellable polymer binder such as polyvinyl alcohol, polyacrylates, polymethacrylates, or poly(vinyl pyrrolidone).
Furukawa et al., U.S. Pat. No. 5,439,739 describes an ink jet recording medium capable of providing recording images having excellent water-resistance, which is obtained by coating a support with a coating containing a water-soluble polymer and a cross-linking agent. The water-soluble polymer is made by copolymerizing a quaternary salt monomer, an amino group-containing monomer or a carboxyl group-containing monomer, and a monomer selected from acrylarmine, 2-hydroxyethyl (meth)acrylate, and N-vinylpyrrolidone. The coating composition may also contain water-soluble polymers such as polyvinyl alcohol, starch, carboxymethyl cellulose, and cationized gelatin. Inorganic pigments such as alumina sol and cationic colloidal silica and polymer particles such as micron-size polystyrene fine particles can be added to the ink-receiving layer.
Williams et al., U.S. Pat. No. 5,494,759 discloses ink jet printing materials comprising a support and an ink receiving layer containing a pigment, a hydrophilic binder comprising a mixture of polyvinylalcohol, polyvinylpyrrolidone, and a vinyl acetate homopolymer and/or vinyl acetate alkyl acrylate copolymer, and a quaternary ammonium compound.
Published Japanese Pat. Kokai 91,981/92 (Mitsubishi Paper Mills, Ltd.) describes a paper cast-coated with a dispersed mixture of silica, a cationic resin, (polydiallyldimethylammonium)chloride, and a binder resin, (polyvinyl alcohol).
Ink jet recording media that have been color-imaged can be used to make film laminates by laminating a layer of transparent polymeric film over the printed image. The polymeric film protects the printed image and gives the image a glossy appearance. Basically, there are two different types of laminate films that can be applied to color-imaged media. One type of laminate film is a pressure-sensitive, adhesive-coated polymeric film. This laminate film can be laminated onto a color-imaged medium at room temperature and is commonly referred to as a “cold laminate film”. Another type of laminate film is a hot-melt, adhesive-coated polymeric film. This type of laminate film must be laminated onto a color-imaged medium at a temperature of 180° F. to 270° F. and is commonly referred to as a “hot laminate film”. Usually, cold laminate films can be laminated onto any color-imaged medium, because the soft and tacky pressure-sensitive adhesive-coating on the laminate film sticks to any imaged surface. However, hot laminate films often do not stick well to color-imaged surfaces, because the absorbed dyes in the ink-receptive coating reduce the adhesion of the hot laminate film to the imaged surface. In such instances, the hot laminate film can delaminate from the imaged medium during subsequent handling.
In view of the foregoing problems with many ink jet recording media, it would be desirable to have a medium capable of providing images having good image quality, waterfastness, smear-resistance, and lightfastness. The medium should also be capable of being laminated with films, particularly hot laminate films, after the medium has been color-imaged. The present invention provides such ink jet recording media.
SUMMARY OF THE INVENTION
The present invention provides an ink jet recording medium comprising a substrate and two ink-receptive coating layers. The first ink-receptive layer comprises a water-soluble polymer and alumina hydrate particulate, and the second ink-receptive layer comprises a blend of water-soluble polymers, wherein at least one of the blended polymers is a quaternary amine-containing polymer. The second ink-receptive coating is coated on the first ink-receptive coating.
The substrate is a paper or polymeric film. Suitable polymeric film substrates include, for example, vinyl, polyethylene, polypropylene, polycarbonate, polyimide, polyester, and fluoroplastic films. The polymeric film may be opaque. Suitable paper substrates include, for example, plain paper, clay-coated paper, resin-coated paper, latex-saturated paper, and polyethylene-coated paper. Preferably, polyethylene-coated paper is used.
The first ink-receptive coating layer contains a water-soluble polymer such as, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, poly(2-ethyl-2-oxazoline), or mixtures thereof Typically, the alumina hydrate particles have a surface area of about 100 to about 200 m
2
/g and an average dispersed particle size of about 40 to about 200 nm. Preferably, the first ink-receptive coating layer comprises about 10 to about 60 dry wt. % of alumina hydrate particles and about 40 to about 90 dry wt. % of poly(2-ethyl-2-oxazoline) and has a thickness of about 5 to about 50 &mgr;m.
The second ink-receptive coating layer contains a water-soluble polymer such as, for example, polyvinyl alcohol, polyvinyl pyrrolidone, or poly(2-ethyl-2-oxazoline) blended with a quaternary amine-containing polymer. Preferably, the quaternary amine-containing polymer is a quaternized vinyl pyrrolidone/dimethylaminoethylmethacrylate copolymer. The second ink-receptive coating may also contain a transitional metal salt such as, for example, a water-soluble copper (II) or cobalt (III) salt, particularly copper (II) sulfate, copper (III) acetate, or cobalt (III) acetate and additives such as optical brighteners and pigments. Preferably, the second ink-receptive coating layer has a thickness of about 0.1 to about 10 &mgr;m.
In a preferred ink jet recording medium of this invention, the bottom layer comprises poly(2-ethyl-2-oxazoline) and alumina hydrate particulate, while the top layer comprises a copolymer of vinyl pyrrolidone and quaternized dimethylaminoethylacrylate, stilbene-based optical brightener, and poly(methyl methacrylate) pigment.
This invention also encompasses film laminates comprising transparent polymeric films and the above-described ink jet recording media. The transparent films are laminated to the second ink-receptive coating layers of the media after the media have been imaged. Suitable transparent polymeric films for laminating onto the imaged media include vinyl, polyethylene, polypropylene, polycarbonate, polyimide, polyester, and fluoroplastic films.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an ink jet record

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