Stock material or miscellaneous articles – Structurally defined web or sheet – Discontinuous or differential coating – impregnation or bond
Reexamination Certificate
1999-11-30
2002-04-16
Schwartz, Pamela R. (Department: 1774)
Stock material or miscellaneous articles
Structurally defined web or sheet
Discontinuous or differential coating, impregnation or bond
C428S423100, C428S522000
Reexamination Certificate
active
06372329
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field Of the Invention
The present invention relates to inkjet recording media suitable for use with dye and pigmented inks. The media comprise a substrate coated with at least two ink-receptive layers. The upper layer comprises a modified poly(vinyl alcohol) compound. The media can record high quality multi-colored images with minimal inter-color bleeding and pigmented ink cracking.
2. Brief Description of the Related Art
In recent years, large (wide) format inkjet recording media have been widely used in outdoor applications such as commercial advertising displays. Outdoor printed media should be capable of projecting high quality multicolored images having good color density, brightness, and sharpness under a variety of weather conditions. Further, outdoor printed media should have good lightfastness and waterfastness.
Generally, most ink-jet recording media comprise a coated substrate such as a paper or polymeric film. Some ink-jet recording media are coated with ink-receptive compositions containing water-soluble polymers which are extremely water-absorptive. Inks used in ink-jet printing devices have traditionally consisted of molecular dyes carried in an aqueous-based ink vehicle. During imaging (i.e., printing), molecular dyes from the ink penetrate into the ink-receptive coating, leaving solvent to evaporate off the surface of the imaged media. Today, pigmented inks are replacing molecular dye-based inks. Pigmented-based inks have better light stability than molecular dye-based inks which is important for outdoor printed media. Pigmented inks comprise a pigmented colorant carried in an aqueous-based ink vehicle. Unlike molecular dyes, pigmented colorants generally bind to and accumulate on the surface of the medium resulting in uneven expansion of the ink-receptive coating. This expansion may cause pigmented ink cracks to appear in the final image. In addition, different colored inks may bleed together causing a loss in color sharpness and smearing.
Some ink-jet recording media are produced by coating a substrate with multiple layers containing various ingredients.
For example, Malhorta, U.S. Pat. No. 5,672,424 discloses a transparency sheet comprising an anionic layer that binds well with the substrate: and a second cationic layer situated on top of the anionic layer that binds with the anionic layer and comprised of cationic quaternary monomers and polymers thereof and a third ink-receiving layer situated on top of the second cationic layer and comprised of block copolymers and graft polymers, a biocide and a filler.
Malhorta, U.S. Pat. No. 5,683,793 discloses a transparency sheet comprising a first coating layer comprised of an ink-absorbing layer and biocide; and a second ink-spreading layer comprised of a hydrophilic vinyl binder, a dye mordant, a filler, and optional lightfastness inducing agent, and an ink spot size increasing agent.
Iqbal et al., U.S. Pat. No. 5,707,722 discloses an ink-jet recording sheet comprising a film substrate bearing on at least one major side surface thereon a two-layer imageable coating system wherein at least one of said layers is microporous, comprising: (1) an absorptive bottom layer comprising at least one crosslinkable polymeric component and at least one water-absorbing hydrophilic polymeric material, and (2) an optically clear top layer comprising at least one nonionic fluorocarbon surfactant having a hydrophilic portion and a hydrophobic portion, and at least one polymer selected from the group consisting of hydroxycellulose and substituted hydroxycellulose polymers, said top layer having been crosslinked on said film substrate by application of heat.
Warner, U.S. Pat. No. 5,747,148 discloses an ink-jet printing sheet having a particle-filled ink-receptor layer and a particle-filled protective-penetrant layer. The particles from both the ink-receptor layer and protective- penetrant layer cause protrusions from the protective penetrant layer.
Edwards et al., U.S. Pat. No. 4,956,230 discloses transparent sheets for use with ink-jet printers and pen plotters. The sheet comprises a transparent coating formed of a blend of at least one hydrophilic polymer containing a carbonylamido functional group and at least one hydrophobic polymer substantially free of acidic functional groups, hydroxyl groups, >NH groups and —NH
2
groups. Several hydrophilic polymers are disclosed such as e.g. poly(N-vinyl pyrrolidone), poly(methyloxazoline), poly(ethyloxazoline).
Sargeant et al., U.S. Pat. No. 5,700,582 discloses a polymer matrix coating used for ink-jet recording media that receives pigmented inks. The polymer matrix coating contains at least one water-soluble component such as poly(2-ethyl-2-oxazoline). The '582 Patent discloses that the polymer matrix coating avoids the problem of pigmented ink cracking.
Hosoi et al., U.S. Pat. No. 5,541,002 discloses a printing paper comprising a paper substrate and a coating layer. The coating comprises a white pigment and a water-soluble resin. The water-soluble resins include poly(vinyl alcohol) derivatives such as fully saponified poly(vinyl alcohol), partially saponified poly(vinyl alcohol), silanol group-modified vinyl alcohol copolymers and the like.
Onishi et al., U.S. Pat. No. 5,662,997 discloses an ink-jet recording film having an ink-receptive layer comprising a poly(vinyl alcohol) having a degree of saponification of 80 to 95% and a degree of polymerization of 1000 to 2000.
Kuroyama et al., U.S. Pat. No. 5,522,968 discloses an ink-jet recording paper having a pH of 6.0 to 8.0 in cold water extraction. The paper is made by applying an alkali metal salt to at least one surface of stack paper containing a filler such as kaolinite, illite, or plastic pigments.
There is a continuous need to develop ink-jet recording media that are capable of forming high quality multi-colored images with minimal inter-color bleeding and ink cracking using pigmented inks. The present invention provides such media.
SUMMARY OF THE INVENTION
The present invention relates to an ink-jet recording medium, suitable for recording images with dye and pigmented inks, comprising a substrate coated with a first ink-receptive layer and a second ink-receptive layer comprising a maleic or itaconic acid-modified poly(vinyl alcohol) and plasticizer. The second layer is coated onto the first layer. Suitable plasticizers phosphates, substituted phthalic anhydrides, glycerols, and glycols, particularly a glycerin trifunctional polyethylene glycol.
Preferably, the coating formulation of the second ink-receptive layer has a pH of no greater than 4.0 prior to being coated onto the first layer, and the pH may be adjusted by using a pH adjuster such as hydrochloric acid, organic hydrogen carboxylate, hydrogen phosphate, sodium hydrogen phthalate, or potassium hydrogen phthalate. The first and second layers may further comprise water-soluble and water-dispersible polymers such as partially hydrolyzed poly(vinyl alcohol), polyoxazoline (e.g., poly(2-ethyl-2-oxazoline) or poly(2-methyl-2-oxazoline) and polyurethanes such as a cationic aliphatic polyurethane, and mixtures thereof. The first layer may contain partially hydrolyzed poly(vinyl alcohol) and aliphatic cationic polyurethane in a ratio in the range of 0.5:1 to 10:1. Generally, in the second layer, the ratio of the maleic or itaconic acid-modified poly(vinyl alcohol) to cationic aliphatic polyurethane is in the range of 1.5:1 to 30:1. The first layer may further comprise an adhesion promoter such as a poly(ethyleneimine)-epichlorohydrin adduct. The first layer may also comprise maleic or itaconic acid-modified poly(vinyl alcohol).
The second layer may comprises a white pigment, organic particulates such as starch, polyolefins, poly(methyl methacrylates), polystyrenes, polytetrafluoroethylenes, and polyurethanes, and additives such as antifoam agents, surfactants, dyestuffs, optical brighteners, and mixtures thereof. Suitable substrates include papers and polymeric films. For example, plain, clay-coated, resin-coated, and latex-saturated papers m
Graczyk Tomasz
Khoultchaev Khizyr K.
Xie Boping
Arkwright Incorporated
Birch & Stewart Kolasch & Birch, LLP
Schwartz Pamela R.
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