Stock material or miscellaneous articles – Composite – Of polyamide
Reexamination Certificate
1998-11-06
2001-02-27
Hess, Bruce H. (Department: 1774)
Stock material or miscellaneous articles
Composite
Of polyamide
C428S195100, C428S500000
Reexamination Certificate
active
06194077
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to an ink receptive material, and more particularly, to waterfast ink receptive coating layer for ink jet recording.
BACKGROUND OF THE INVENTION
The quality of waterfastness is of primary importance for today's ink jet media products. The term “waterfast” may be defined as the quality of being impervious to the effects of water. Products normally used out of doors, such as billboards, signs, etc., require protection from typical outdoor moisture sources such as rain, humidity, etc. Traditionally, non-waterfast ink jet film products have been laminated at high cost in order to enable outdoor usage. Ink jet office products also require waterfast properties to protect the printed image from typical indoor moisture sources such as humidity or the occasional spilled cup of coffee, etc.
Previous efforts to prepare waterfast ink jet film media involved mixing water-soluble polymer binders with water-soluble dye-fixing agents in an ink-receptive coating layer for an ink jet medium. While this approach can impart a certain amount of dye-fixing capability to the media, it does not give a substantially waterfast media. This is because most of the polymer binders and dye-fixing agents are water-soluble and do not give good wet adhesion to the base substrate. As a result, when contacted with water, these coatings swell and come off the substrates.
U.S. Pat. No. 5,439,739 discloses an ink jet recording medium comprising a support and at least one ink jet receiving layer, said ink receiving layer comprising a water-soluble polymer obtained by co-polymerizing 10-50 parts by weight of a quaternary salt monomer, 1-30 parts by weight of an amino group containing monomer or a carboxyl group containing monomer and 20-80 parts by weight of a monomer selected from acrylamide, methacrylamide, N,N-dimethacrylamide, N-isopropylacrylamide, diacetone acrylamide, N-methylolacrylamide, 2-hydroxyethyl-(meth)acrylate, and N-vinylpyrrolidone, and 0.1-30 parts by weight of a cross-linking agent.
U.S. Pat. Nos. 5,472,789 and 5,389,723 disclose a liquid-absorbent composition comprising a blend of (a) at least one polymeric matrix component comprising a cross-linkable polymer derived from &agr;, &bgr;-ethylenically unsaturated monomers, (b) at least one polymeric liquid-absorbent component, (c) polyfunctional aziridine as a crosslinking agent, said composition capable of forming semi-interpenetrating networks wherein said at least one polymeric matrix component is crosslinked and said at least one liquid-absorbent component is uncrosslinked, said uncrosslinked liquid-absorbent component being able of being dissolved in the liquid that it is capable of absorbing.
U.S. Pat. No. 4,649,064 claims an ink-receiving layer containing (a) a hydrophilic cross-linkable film-forming material which is crosslinked to a degree sufficient to render it waterfast, while permitting it to rapidly absorb a water-based ink, (b) a crosslinking agent that is capable of crosslinking a cross-linkable colorant/resin composition in a water-based liquid ink.
WO 96/18496 discloses a water resistant ink jet receiving medium comprising an ink receptive layer of a crosslinked vinyl amide acrylic acid or methacrylic acid or ester thereof random copolymer and a cationic resin.
U.S. Pat. No. 5,532,064 discloses an ink-absorption layer having crosslinked gelatin in admixture with an amide in low concentration, generally less than approximately 1% or 2% by weight.
U.S. Pat. No. 4,701,837 discloses an ink-receiving layer mainly containing a water-soluble polymer and a crosslinking agent.
U.S. Pat. No. 5,206,071, entitled “Archivable Ink Jet Recording Media,” discloses film media that are useful in ink jet printing, and which comprise a transparent, translucent or opaque substrate, having on at least one side thereof a water-insoluble, water-absorptive and ink-receptive matrix, said matrix comprised of a hydrogel complex and a polymeric high molecular weight quaternary ammonium salt.
U.S. Pat. No. 5,474,843 and WO 95/16561 disclose an ink-accepting coating layer containing (a) a water-soluble mordant that forms an insoluble compound with, and immobilizes the dyestuffs of, the ink jet inks, (b) a water-absorbing solid polymer, wherein said polymer has been rendered insoluble in water at room temperature by chemical hardening of said polymer at elevated temperature in an aqueous coating solution prior to coating of said coating solution, and (c) non-porous polymer beads dispersed in said water-absorbing polymer in an uppermost layer of said ink-accepting composition.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an ink receptive coating layer for ink jet recording that is waterfast while also having good water absorptivity, good dye-fixing capability and good adhesion to the base substrate. It is a further object of the present invention to provide a water-insoluble ink receptive material that is comprised of the coating layer applied to a substrate.
The present invention provides a water-insoluble ink receptive coating comprising a gelatin and a water-insoluble quaternary cationic polymer which are cross-linked together with a multifunctional cross-linking agent. Furthermore, a pigment is contained in the ink receptive coating to make a matted or non-tacky ink jet recording medium.
DETAILED DESCRIPTION
In the present invention, a gelatin binder, and a water-insoluble quaternary cationic polymer are cross-linked together with a multifunctional cross-linking agent to form a water-insoluble ink receptive coating for ink jet recording. The ink receptive coating may also contain a pigment to make a matted or non-tacky ink jet recording media. The ink jet coating thus formed may be characterized as having an interpenetrating polymer network (IPN) which imparts to the layer the properties of waterfastness, water absorptivity, and an ability to adhere well to the base substrate.
In order to achieve an IPN with the balanced properties of good wet adhesion, water absorptivity and waterfastness, and balanced cross-linking density, the gelatin, the water-insoluble quaternary cationic polymer, and the multifunctional cross-linking agent of the ink receptive coating layer of the present invention are selected as set forth in the following detailed description.
The gelatin binder that is selected should possess reactive functional groups that can react with the multifunctional cross-linking agent to form the IPN with the water-insoluble quaternary polymer. The gelatin binder imparts good water absorptivity to the ink-receptive coating. The nature of gelling at room temperature makes it a good candidate for making water-insoluble coating.
The gelatin may be a gelatin having a Bloom number from about 100 to about 300 with viscosity from 3.0 to 55 mPa.s. Further, the gelatin may be derived from an acid treated precursor or an alkali treated precursor.
In the inventive water-insoluble ink receptive materials, the content of gelatin in the ink receptive coating layer is from about 30% to about 90%, by weight based on the total weight of the coating layer. Preferably, the content of gelatin in the dried coating is from about 50% to about 70%, by weight based on the total weight of the coating layer.
In the present invention, the water-insoluble quaternary cationic polymer is defined as a quaternary cationic polymer that remain undissolved after immersion in water for 24 hours. This is the key difference from U.S. Pat. No. 5,474,843 and all other patents in which water soluble quaternary cationic polymers or mordants were used. It is the gelling property of gelatin, water insolubility of the quaternary cationic polymer, and the IPN structure due to the crosslinking that gives the materials of the instant invention a balanced image quality and waterfastness. Table I lists the solubility of the most widely used quaternary cationic polymers.
TABLE I
Solubility of Various Quaternary Cationic Polymer Mordants
Cationic Mordant
Solubility in water*
Notes
Syntran Hx31-44 & 31-65
Insoluble
Prese
Nguyen Khanh
Sargeant Steven J.
Yuan Shengmei
Arkwright Incorporated
Birch & Stewart Kolasch & Birch, LLP
Hess Bruce H.
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