Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention relates to an improved recording element for ink jet printing.
• ink jet printing has become a popular technique because of its simplicity, convenience and low cost. Especially in those instances where a limited edition of the printed matter is needed ink jet printing has become a technology of choice.
• a recent survey on progress and trends in ink jet printing technology is given by Hue P. Le in Journal of Imaging Science and Technology Vol. 42 (1), Jan/Febr 1998.
• ink jet printing tiny drops of ink fluid are projected directly onto an ink receptor surface without physical contact between the printing device and the receptor.
• the printing device stores the printing data electronically and controls a mechanism for ejecting the drops image-wise. Printing is accomplished by moving the print head across the paper or vice versa.
• Early patents on ink jet printers include US 3,739,393, US 3,805,273 and US 3,891,121.
• the jetting of the ink droplets can be performed in several different ways.
• a continuous droplet stream is created by applying a pressure wave pattern. This process is known as continuous ink jet printing.
• the droplet stream is divided into droplets that are electrostatically charged, deflected and recollected, and into droplets that remain uncharged, continue their way undeflected, and form the image.
• the charged deflected stream forms the image and the uncharged undeflected jet is recollected.
• several jets are deflected to a different degree and thus record the image (multideflection system).
• the ink droplets can be created “on demand” (“DOD” or “drop on demand” method) whereby the printing device ejects the droplets only when they are used in imaging on a receiver thereby avoiding the complexity of drop charging, deflection hardware, and ink recollection.
• DOD on demand
• the ink droplet can be formed by means of a pressure wave created by a mechanical motion of a piezoelectric transducer (so-called “piezo method”), or by means of discrete thermal pushes (so-called “bubble jet” method, or “thermal jet” method).
• Ink compositions for ink jet typically include following ingredients : dyes or pigments, water and/or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders, preservatives, etc.. It will be readily understood that the optimal composition of such an ink is dependent on the ink jetting method used and on the nature of the substrate to be printed.
• the ink compositions can be roughly divided in :
• Pigments and particles have also been described in patent applications including DE 2,925,769, GB 2,050,866, US-P 4,474,850, US-P 4,547,405, US-P 4,578,285, WO 88 06532, US-P 4,849,286, EP 339604, EP 400681, EP 407881, EP 411638 and US-P 5,045,864 (non-exhaustive list).
• binders of which the most common types are gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, and various types of cellulose derivatives. These conventional binders are mentioned in numerous patent documents.
• the present invention extends the teachings on ink-absorptive pigments in ink jet recording media.
• an ink jet recording element comprising a support and an ink receiving layer containing a binder and Ca 3 (PO 4 ) 2 pigment characterized in that said Ca 3 (PO 4 ) 2 pigment consists substantially of the whitlockite crystal structure.
• the pigment incorporated in the ink receiver layer is calcium phosphate (Ca 3 (PO 4 ) 2 ) substantially completely composed of the so-called whitlockite crystal structure, also called ⁇ -calcium triphosphate ( ⁇ -CTP), which is a rhombohedral crystal structure.
• ⁇ -CTP ⁇ -calcium triphosphate
• Crystal structures which also can deviate stoechiometrically from Ca 3 (PO 4 ) 2 may be present, such as apatite, hydroxylapatite, monetite, etc..
• the nature of the crystal srtucture(s) present can be verified by means of X-ray diffraction XRD.
• the preparation of calcium phosphate of the whitlockite structure is described a.o. in US-P 5,939,039. Scientific publications on whitlockite type calcium phosphate and derivatives include : Lazoryak et al., "Triple phosphates of calcium, sodium, and trivalent elements with whitlockite-like structure", Mater. Res. Bull.
• Calcium phosphate particles of whitlockite crystal type may be used in any of the orthopaedic or dental applications known for the use of calcium phosphate, such as bone filling defect repair, oncological defect filling, dental extraction site filling, and potential drug delivery applications. See, for instance, Jarcho et al., "Synthesis and fabrication of ⁇ -tricalcium phosphate (whilockite) ceramics for potential prosthetic applications", J. Mater. Sci. (1979), 14(1) 142-50.
• the whitlockite type calcium phosphate is the sole pigment of the ink receiving layer.
• it may be mixed with some other well-known pigments such as silica, talc, clay, koalin, diatomaceous earth, calcium carbonate, magnesium carbonate, aluminium hydroxide, aluminium oxide, titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, satin white, boehmite and pseudo-boehmite, or organic particles such as polystyrene, polymethylmethacrylate, silicones, urea-formaldehyde condensation polymers, polyesters and polyamides.
• the binder can be chosen from a list of compounds well-known in the art including hydroxyethyl cellulose; hydroxypropyl cellulose; hydroxyethylmethyl cellulose; hydroxypropyl methyl cellulose; hydroxybutylmethyl cellulose; methyl cellulose; sodium carboxymethyl cellulose; sodium carboxymethylhydroxethyl cellulose; water soluble ethylhydroxyethyl cellulose; cellulose sulfate; polyvinyl alcohol; vinylalcohol copolymers; polyvinyl acetate; polyvinylacetal; polyvinyl pyrrolidone; polyacrylamide; acrylamide/acrylic acid copolymer; styrene/acrylic acid copolymer; ethylene-vinylacetate copolymer; vinylmethyl ether/maleic acid copolymer; poly(2-acrylamido-2-methyl propane sulfonic acid); poly(diethylene triamine-co-adipic acid); polyvinyl pyridine; polyvin
• a preferred binder for the practice of the present invention is polyvinyl alcohol (PVA).
• the total dry coating weight of the receiving layer is preferably comprised between 10 and 40 g/m 2 .
• a cationic substance acting as mordant may be present in the ink receiving layer.
• Such substances increase the capacity of the layer for fixing and holding the dye of the ink droplets.
• a particularly suited compound is a poly(diallyldimethylammonium chloride) or, in short, a poly(dadmac). These compounds are commercially available from several companies, e.g. Aldrich, Calgon, Clariant, BASF, EKA Chemicals, and Nippon Goshei.
• a preferred type is GOHSEFIMER K210, trade name of Nippon Goshei Co..
• dadmac copolymers such as copolymers with acrylamide; dimethylamine-epichlorohydrine copolymers,
• CYPRO 514/515/516, SUPERFLOC 507/521/567 cationic cellulose derivatives such as CELQUAT L-200, H-100, SC-240C, SC-230M, trade names of Starch & Chemical Co., and QUATRISOFT LM200, UCARE polymers JR125, JR400, LR400, JR30M, LR30M and UCARE polymer LK; fixing agents from Chukyo Europe: PALSET JK-512, PALSET JK512L, PALSET JK-182, PALSET JK-220, WSC-173, WSC-173L, PALSET JK-320, PALSET JK-320L and PALSET JK-350; polyethyleneimine and copolymers, e.g.
• LUPASOL trade name of BASF AG
• triethanolamine-titanium-chelate e.g. TYZOR, trade name of Du Pont Co.
• copolymers of vinylpyrrolidone such as VIVIPRINT 111, trade name of ISP, a methacrylamido propyl dimethylamine copolymer; with dimethylaminoethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trade names of ISP
• vinylimidazole e.g.
• LUVIQUAT CARE, LUVITEC 73W, LUVITEC VP155 K18P, LUVITEC VP155 K72W, LUVIQUAT FC905, LUVIQUAT FC550, LUVIQUAT HM522, and SOKALAN HP56 all trade names of BASF AG; polyamidoamines, e.g. RETAMINOL and NADAVIN, trade marks of Bayer AG; and phosphonium compounds such as disclosed in EP 609930.
• Still other cationic compounds include gelatin when the layer pH is below the isoelectric point of the gelatin, cationic aluminum oxide, boehmite, and poly(aluminumhydroxychloride) such as SYLOJET A200, trade name of Grace Co..
• Still further cationic polymers include polyvinylamines, e.g. PVAM-0595B from Esprit Co., and cationic modified acrylics, e.g. ACRIT RKW319SX, trade name of Tasei Chemical Industries, and RD134 from Goo Chemical.
• the cationic substance is not incorporated in the ink receiving layer itself but in a separate thin top layer.
• this layer is coated from an aqueous medium. Its dry coverage is preferably comprised between 0.5 and 5 g/m 2 .
• the cationic mordant can also be distributed between the ink receiving bulk layer and the extra thin top layer.
• an extra adhesive layer may be applied between the support and the ink receiving layer (undercoat layer).
• This layer is then coated from an aqueous medium containing any of the numerous known adhesive polymers.
• Preferred adhesive polymers include styrene-butadiene latex, acrylate latices, such as ethylacrylate-hydroxyethylmethacrylate, poly (ethylene-vinylacetate), polyvinylesters, copolyesters, and polyurethanes.
• the dry coating weight of this undercoat layer when present is preferably comprised between 0.5 and 10 g/m 2 .
• the ink receiving layer and the optional top- and undercoat layers may further contain well-known conventional ingredi ⁇ nts, such as surfactants serving as coating aids, hardening agents plasticizers, whitening agents and matting agents.
• Surfactants may be incorporated in the ink-receiving layer of the present invention. They can be any of the cationic, anionic, amphoteric, and non-ionic ones as described in JP-A 62-280068 (1987).
• the surfactants are N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, ⁇ -olefin sulfonic acid salts, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, alkylether sulfonic acid salts, alkylallylethersulfonic acid salts, alkylamidesulfonic acid salts, alkylphosphoric acid salts, alkyletherphosphoric acid salts, alkyl
• Useful cationic surfactants include N-alkyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, ethoxylated alkyl guanidine-amine complex, oleamine hydroxypropyl bistrimonium chloride, oleyl imidazoline, stearyl imidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, cocotrimonium chloride, alkyl polyglycolether ammonium sulphate, ethoxylated oleamine, lauryl pyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyl dimethylamine lactate, coconut fatty amide, oleyl hydroxyethyl imidazoline, isostearyl ethylimidonium ethosulphate, lauramidopropyl PEG-d
• These surfactants are commercially available from DuPont and 3M.
• the concentration of the surfactant component in the ink-receiving layer is typically in the range of 0.1 to 2 %, preferably in the range of 0.4 to 1.5 % and is most preferably 0.75 % by weight based on the total dry weight of the layer.
• the ink-receiving layer according to this invention may be crosslinked to provide such desired features as waterfastness and non-blocking characteristics.
• the crosslinking is also useful in providing abrasion resistance and resistance to the formation of fingerprints on the element as a result of handling.
• crosslinking agents also known as hardening agents - that will function to crosslink film forming materials. Hardening agents can be used individually or in combination and in free or in blocked form.
• a great many hardeners, useful for the present invention are known, including formaldehyde and free dialdehydes, such as succinaldehyde and glutaraldehyde, blocked dialdehydes, active esters, sulfonate esters, active halogen compounds, isocyanate or blocked isocyanates, polyfunctional isocyanates, melamine derivatives, s-triazines and diazines, epoxides, active olefins having two or more active bonds, carbodiimides, isoxazolium salts subsituted in the 3-position, esters of 2-alkoxy-N-carboxy-dihydroquinoline, N-carbamoylpyridinium salts, hardeners of mixed function, such as halogen-substituted aldehyde acids (e.g.
• mucochloric and mucobromic acids onium substituted acroleins and vinyl sulfones and polymeric hardeners, such as dialdehyde starches and copoly(acroleinmethacrylic acid), and oxazoline functional polymers, e.g. EPOCROS WS-500, and EPOCROS K-1000 series.
• boric acid is a preferred crosslinker.
• the ink-receiving layer of the present invention may also comprise a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalicanhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, n-methyl-2-pyrrolidone, n-vinyl-2-pyrrolidone.
• a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromo
• the ink-receiving layer of the present invention may also comprise ingredients to improve the lightfastness of the printed image, such as antioxidants, UV-absorbers, peroxide scavengers, singlet oxygen quenchers such as hindered amine light stabilizers, (Hals compounds) etc..
• ingredients to improve the lightfastness of the printed image such as antioxidants, UV-absorbers, peroxide scavengers, singlet oxygen quenchers such as hindered amine light stabilizers, (Hals compounds) etc.
• the ink receiving layer and the optional supplementary layers can be coated onto the support by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating.
• the support for use in the present invention can be chosen from the paper type and polymeric type support well-known from photographic technology.
• Paper types include plain paper, cast coated paper, polyethylene coated paper and polypropylene coated paper.
• Polymeric supports include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
• PET polyethylene terephthalate
• Other examples of useful high-quality polymeric supports for the present invention include opaque white polyesters and extrusion blends of polyethylene terephthalate and polypropylene. Polyester film supports, and especially polyethylene terephthalate, are preferred because of their excellent properties of dimensional stability.
• Typical supports for outdoor use include PET, wet strength paper, PVC, PVC with an adhesive backing, the polyethylene paper TYVEK, trade name of Du Pont Co., the porous polyethylene paper TESLIN, trade name of International Paper CO., canvas, polypropylene, and polycarbonate.
• a Ca 3 (PO 4 ) 2 powder commercially available and made by Merck was first milled by means of a sand mill (Spangenberg) using zirconium silicate pearls of 0.6 mm. The grinding took place during 6 hours leading to Ca 3 (PO 4 ) 2 pigments with a particle size between 1 and 2 ⁇ m. After the milling the pearls were separated from the pigment by filtering and washing with water. The pigment content of the slurry amounted to 12% (by weight). The pigment was a heterogeneous mixture of different crystal structures, as was demonstrated by XRD.
• a coating liquid for forming an ink recording layer was prepared by adding 5 parts by solid weight of a 10% aqueous solution of polyvinyl alcohol (POVAL 117, trade mark of K.K. Kuraray) to 94.5 parts by solid weight of the prepared Ca 3 (PO 4 ) 2 dispersion. Finally, 0.5 parts by solid weight of boric acid solution was added as crossslinker.
• POVAL 117 polyvinyl alcohol
• boric acid solution was added as crossslinker.
• the resultant coating liquid had a total solid content of 11.2% by weight.
• the coating solution was coated on a subbed PET sheet (100 ⁇ m) using a coating knife to form an ink receiving layer having a dry weight of 28 g/m 2 , and dried at 40°C. As is shown by the nitrogen gas adsorption method the pore volume of the layer is only 0.07 ml/g.
• An ink jet recording medium was produced by the same procedures as in Example 1 with the following exception.
• the polyvinyl alcohol was replaced by a cation - modified polyvinyl alcohol (GOHSEFIMER K210, trade mark of Nippon Gohsei). The test results are shown in table 1.
• An ink jet recording medium was produced by the same procedures as in Example 1 with the following exception.
• the Ca 3 (PO 4 ) 2 was replaced by a porous type of whitlockite crystal structure, as verified by XRD, (source Orthovita Inc.).
• the pore volume of the layer is 0.39 ml/g, much higher than for the comparative example. Further test results are shown in table 1.
• An ink jet recording medium was produced by the same procedures as in Example 2 with the following exception.
• the Ca 3 (PO 4 ) 2 was replaced by a porous type of whitlockite crystal structure, as verified by XRD, (source Orthovita Inc.). The test results are shown in table 1.
• porous Ca 3 (PO 4 ) 2 leads to an important improvement of the drying time and inter color bleeding.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Ink Jet (AREA)

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Citations (3)

• 2001
  • 2001-07-03 EP EP20010000266 patent/EP1273455B1/de not_active Expired - Lifetime
  • 2001-07-03 DE DE2001602683 patent/DE60102683T2/de not_active Expired - Fee Related
• 2002
  • 2002-07-01 JP JP2002191867A patent/JP2003103925A/ja active Pending

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