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
• • 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
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/508—Supports
• • 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
  • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
• • 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
  • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• • 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

• This invention relates to image-recording elements that contain a polymeric substrate on which are coated ink-receptive layers that can be imaged by the application of liquid ink dots (e.g. by ink-jet printers).
• Non impact printing technologies are becoming very popular in the arena of hard copy materials.
• ink jet printing is one of the technologies which is gaining most of the attention. This is primarily due to the availability of very low cost ink jet printers with multi-colour possibilities and very acceptable quality.
• the individual ink droplets can be applied to the receiving substrate in several different ways.
• the ink solution can be jetted continuously through a small nozzle towards the receiving layer (Hertz method).
• the ink droplet can also be created "upon demand” by a piezoelectric transducer or a thermal push (Bubble Jet).
• Polymeric substrates are becoming more important in the manufacture of high-quality receiving elements for ink-jet printing (e.g. resin coated paper, polyesterfilm, etc).
• Most methods for ink jet printing do however use an aqueous or polar ink composition that does not absorb well in the polymeric substrate material.
• all ink jet printing processes using aqueous based inks do require a special treatment of the polymeric substrate material in order to be useful for practical purposes.
• an additional ink-receiving layer must be applied in order to obtain a material with an acceptable ink absorption speed.
• a dimensionally stable substrate such as polyethyleneterephtalate (PET), cellulosetriacetate, or PE-extruded paper is used most frequently and coated with one or more polymer coatings.
• PET polyethyleneterephtalate
• cellulosetriacetate cellulosetriacetate
• PE-extruded paper is used most frequently and coated with one or more polymer coatings.
• These ink-receiving polymer coatings comprise one or more binders and different additives which are necessary to meet the requirements mentioned above.
• US-P 4,503,111 describes an image receiving layer where a first binder (gelatin or polyvinylalcohol (PVA)) is mixed with a polyvinylpyrrolidone (PVP) having a molecular weight of at least 90000, and for which the ratio PVA/PVP is in the range 3:1 to 1:3.
• PVA polyvinylalcohol
• PVP polyvinylpyrrolidone
• the drying time characteristic can also be improved by a better tuning of the pH value of the coating solution, as described in EP-A 594 896.
• the image-recording elements with ink-receiving layers that have been described in the prior art do improve the water absorption of the layers but fail more or less to combine a short drying time with a small dry coating thickness of the (mainly hydrophilic) ink-receiving layer.
• a thick ink-receiving layer does show bad properties regarding humidity dependent curl and so on.
• water based or “aqueous” ink compositions within the scope of the present invention has to be understood an ink wherein at least 50 % by weight of the total solvent content is water.
• the properties of the - receiving layer are described as universal. I.e. once a quality level was reached for printing using a specific water based ink composition, the prior art suggests that the use of any water based ink compositions would give rise to the same quality.
• the present invention is based upon the discovery that a short drying time characteristic for a given ink-receiving layer and a given water based ink composition is obtained if the layer shows a fast ink absorption speed when immersed in said water based ink composition and provided that the ink-receiving layer thickness is situated in a given range.
• ink jet systems according to the present invention is the fact that an ink-receiving layer with low thickness can be provided that shows, for a given water based ink composition, equal to to better drying time characteristics than thicker ink-receiving layers.
• the ink-receiving layers in the novel image-recording elements according to this invention contain at least a binder which may be selected from the group consisting of: (1) hydroxyethyl cellulose; (2) hydroxypropyl cellulose; (3) hydroxyethylmethyl cellulose; (4) hydroxypropyl methyl cellulose; (5) hydroxybutylmethyl cellulose; (6) methyl cellulose; (7) sodium carboxymethyl cellulose; (8) sodium carboxymethylhydroxethyl cellulose; (9) water soluble ethylhydroxyethyl cellulose; (10) cellulose sulfate; (11) polyvinyl alcohol; (12) polyvinyl acetate; (13) polyvinylacetal; (14) polyvinyl pyrrolidone; (15) polyacrylamide; (16) acrylamide/acrylic acid copolymer; (17) styrene/acrylic acid copolymer; (18) ethylene-vinylacetate copolymer; (19) vinylmethyl ether/maleic acid cop
• the ink-receiving layer coatings according to the present invention may also comprise as binder :
• Preferred binary blends of binders for the ink-receiving layers according to this invention are :
• Preferred ternary blends of binder materials for coating the ink-receiving layers according to this invention are :
• Preferred binders are gelatin, vinylpyrrolidone and polyvinylalcohol or binary or ternary blends of these.
• Gelatin is thus a particularly preferred material for use in forming the ink-receiving layer of materials according to this invention.
• reasons is the fact that it forms a clear coating, is readily cross-linked in an easily controllable manner, and is highly absorptive of water-based liquid inks to thereby provide rapid-drying characteristics.
• Dry ink-receiving layers according to the present invention therefor comprise most preferably at least 30 % by weight of gelatin with respect to the weight of all ingedients in said ink-receiving layer.
• the ink-receiving layer according to this invention is preferably cross-linked to provide such desired features as waterfastness and non-blocking characteristics.
• the cross-linking is also useful in providing abrasion resistance and resistance to the formation of fingerprints on the element as a result of handling.
• cross-linking agents also known as hardening agents - that will function to cross-link film forming materials, and they are commonly used in the photographic industry to harden gelatin emulsion layers and other layers of photographic silver-halide elements.
• 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, s-triazines and diazines, epoxides, active olefins having two or more active bonds, active olefins, carbodiimides, isoxazolium salts unsubsituted in the 3-position, esters of 2-alkoxy-N-carboxy-dihydroquinoline, N-carbamoyl and N-carbamoylpyridinium salts, hardeners of mixed function, such as halogen-substituted aldehyde acids (e.g. mucochloric and mucobromic acids), onium substituted acrole
• the ink-receiving layers comprising at least 30 % by weight of gelatin with respect to the weight of all ingedients in said ink-receiving layer according to the present invention are most preferably hardened by formaldehyd that is applied in an amount of 0.001 to 0.05 parts pro part of gelatine present.
• the ink-receptive layer in the novel image-recording elements according to this invention may also comprise particulate material, both porous and non-porous, which may consist either of primary particles comprising single particles or of porous particles comprising secondary particles formed from aggregation of the primary particles.
• particulate material particularly preferrable are porous particles.
• Most preferably said porous particles have an average particle size from 1 to 30 ⁇ m, preferably from 3 to 10 ⁇ m which can be formed by aggregation of smaller particles, having a size of 0.01 to 2 ⁇ m, preferably 0.1 to 0.5 ⁇ m. These porous particles formed by secondary or tertiary aggregation will not easily desintegrate.
• the porous material is preferably made of at least one of the organic materials such as polystyrene, polymethacrylate, polymethylmethacrylate, elastomers, ethylene-vinyl acetate copolymers, polyesters, polyester-copolymers, polyacrylates polyvinylethers, polyamides, polyolefines, polysilicones, guanamine resins, polytetrafluoroethylenes, elastomeric styrene-butadiene rubber (SBR), elastomeric butadiene-acrylonitrile rubber (NBR), urea resins, urea-formalin resins, etc., or inorganic materials such as synthetic 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, aluminium silicate,
• Polymethylmethacrylate beads may be added as matting agents. They are usually added to the receptive layer in a range of 0.4 to 1.2 g/m2 and preferably in a range of 0.40 to 0.90 g/m2 with 0.50 g/m2 being most preferred.
• the ink-receiving layer of the invention may contain a whitening agent.
• TiO2 rutile or anatase
• Amounts of whitener present in the film element can range from 0.1 to 5.0 g/m2, and preferably from 0.2 to 2.0 g/m2, and most preferably 0.3 g/m2.
• a slurry of the whitener may be added by batchwise addition or by in-line injection just prior to coating the receptor layer(s) on the support.
• the ink-receiving layer of the present invention can 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, and polymer latices with low Tg-value such as polyethylacrylate, polymethylacrylate, etc.
• a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin,
• Surfactants may be incorporated in the ink-receptive layer of the present invention. They can be any of the cationic, anionic, amphoteric, and nonionic ones as described in JP-62-280068 (1987).
• the surfactants are soap, N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, a-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, alkylallyl
• These surfactants are commercially available from DuPont and 3M.
• the concentration of the surfactant component in the ink-receptive layer is typically in the range of 0.1 to 2 percent, preferably in the range of 0.4 to 1.5 percent and is most preferably 0.75 percent by weight based on the total dry weight of the layer.
• the image-receiving layers of the present invention may additionally comprise mordanting polymers such as ammonium and/or phosphonium moiety containing polymers.
• mordanting polymers such as ammonium and/or phosphonium moiety containing polymers.
• Very appropriate polymers containing phosphonium moieties are described in EP-A 609 930.
• said ink-receiving layer comprises two distinct layers wherein at least one layer comprises a polymer containing a phosphonium moiety.
• the image-receiving layers of the present invention may additionally comprise different additives which are well known in the art, and include UV-filters and antistatic agents.
• the coating composition for ink-receiving layers according to the present invention comprise at most 7 % by weight of an hydrophilic polymer or polymer blend.
• the image-recording elements of this invention comprise a polymeric support or a PE-coated paper support for the ink-receptive layer.
• polymeric supports include, for example, transparent supports as those used in the manufacture of photographic films including cellulose acetate propionate or cellulose acetate butyrate, polyesters such as poly(ethyleneterephthalate), poly(ethylenenaphthalate) and polyesters comprising recurring units containg hydrophilic groups e.g. sulfoisophthalic acid, sulfonated diols, etc., polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
• polyesters and extrusion blends of poly(ethylenenterephthalate) and polypropyleen examples include opaque white polyesters and extrusion blends of poly(ethylenenterephthalate) and polypropyleen.
• Polyester film supports and especially poly(ethyleneterephthalate) are preferred because of their excellent properties of dimensional stability.
• a subbing layer must be employed to improve the bonding of the ink-receptive layer to the support.
• subbing layers for this purpose are well known in the photographic art and include, for example, polymers of vinylidene chloride such as vinylidene chloride/acrylonitrile/acylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
• the subbing layer can also be a chlorine free subbing layer as described in e.g. EP-A 078 559 and EP-A 559 244.
• the subbing layer can also be a antistatic subbing layer comprising a polythiophene derivative as described in e.g. EP-A 602 713.
• the image-recording elements of this invention are employed in printing processes where liquid ink dots are applied to the ink-receiving layer of the element.
• a typical process is a ink-jet printing process which involves a method of forming the image on a paper or transparency by ejecting ink droplets from a print head from one or more nozzles.
• Several schemes can be used to control the deposition of the ink droplets on the image-recording element to form the desired ink dot pattern used to build the image.
• one method comprises deflecting electrically charged ink droplets by electrostatic means.
• Another method comprises the ejection of single droplets "upon demand" under the control of a piezoelectric device which can operate by volume change or "wall” motion, or under the control of a thermal excitation.
• the inks used to image the image-recording elements of this invention comprise at least 2 % by weight of humectants containing hydroxyl moieties and also at least 0.2 % by weight of viscosity regulators wherein the main solvent is water.
• the composition of the inks for the image-recording elements of the present invention are specifically tuned for obtaining a good value regarding a and b parameters if tested for the behaviour according to the equation described above.
• the inks in the present invention can also contain additional ingredients, which are well known to those skilled in the art, including surface tension regulators, preservatives, organic solvents, etc...
• the dyes used in these ink-jet ink compositions are typically water-soluble direct dyes or acid type dyes, although also pigmented inks fall within the scope of the present invention.
• a small film sample of ink-receiving element was placed upon a vacuum table made of porous metal and fixed to it by switching on the vacuum to provide a flat surface.
• an open ended metal cylinder was placed on top of the ink-receiving layer.
• the whole apparatus was conditioned at 25°C and the thickness of the dry film sample was measured using a quartz tube with an ending radius of 10.73 mm and a load of 6.0 g upon the dry layer, said tube connected to an inductive measuring probe giving, after amplification, an electrical signal corresponding with the actual position of the surface of the layer.
• This device was operated on a time-base scale wherein every second the actual measurement was done during 25 ms and the measurement lasted for 30 sec to give 30 measurements of the thickness of the dry layer.
• the thickness of the dry layer was determined by averaging the tickness values obtained by the 30 measurements.
• the quartz tube was removed from the film and the ink composition under study was poored into the open ended cylinder to be able to penetrate the layer. After pooring said ink composition into the cylinder the quartz tube was replaced and the tickness was again measured on a time-base scale wherein every second the actual measurement was done during 25 ms and the measurement lasted for 120 sec. Every second the thickness (expressed in ⁇ m) of the ink-receiving layer absorbing the ink composition was captured with a datalogging system. From these 120 measurements the thickness of the dry layer was subtracted, giving 120 values of ⁇ d. These values were fitted to equation (I) and the values of a and b for the combination ink-receiving layer/ink composition under study determined.
• MEASUREMENT B determination of the roughness of the surface
• the roughness of the surface of the receiving layers was measured with a Perthometer S6p with measuring probe RTK50 according to ANSI, ASME B 46.1-1985 and referred to as Roughness Average, Ra.
• a polyethylene terephthalate film (PET-100 ⁇ m thick with typical photographic subbing layers, used for a better bonding between the PET and the gelatinous layers) was used as the substrate.
• An ink-receiving element with an ink-receiving layer was prepared as described for element 1, except for the fact that in coating composition A 70 parts of gelatin were used in stead of only 50 parts. The ink-receiving layer was coated directly, without any dilution, from this more concentrated solution.
• a recording medium with an ink-receiving layer was prepared as described for element 1, except for the fact that coating composition B was used instead of coating composition A.
• an ink-receiving layer consisting of 2 layers (A and B) was coated by simultaneously applying to one side of the substrate a layer with coating composition B and a layer with coating composition C on a pilot coating machine with layer B being the outermost layer.
• Coating composition C differed from coating composition B in that only 19 parts of gelatin were used and combined with 18 parts of polyvinylpyrrolidone (LUVISKOL K90, a tradename for polyvinylpyrrolidone with a MW of 630000, commercially available from BASF AG, Germany), and 0.5 parts of detergent.
• the coatings were chilled at 5°C for 20 seconds, dried at 35°C for 280 seconds at 30% relative humidity, so as to give a dry film coating thickness of 5.3 micron for each layer.
• a recording medium with an ink-receiving layer was prepared as described in example 2, except for the fact that in coating composition A gelatin was replaced by hydroxyethylcellulose (CELLOSIZE WP09H, a tradename for a low molecular weight hydroxyethylcellulose, commercialy available from Union Carbide, USA).
• the coating was chilled at 5°C for 20 seconds, dried at 35°C for 400 seconds at 30% relative humidity, so as to give a dry film coating thickness of 21.4 micron.
• a recording medium with an ink-receiving layer was prepared as described for element 1, except for the fact that coating composition D was used to obtain a dry coating thickness of 2.4 micron (element 8) and 12.0 micron (element 9), element 9 being dried for 400 seconds and element 8 for 220 sec.
• a Polyvinylalcohol (MOWIOL 8-88, a tradename for polyvinylalcohol with a degree of hydrolysis of 88 mol. % and a molecular weight of 49000 (Mw), commercialy available through the Hoechst Company, Germany) were mixed with 25 parts of Polyvinylpyrrolidone (LUVISKOL K90, a tradename for polyvinylpyrrolidone with MW 630,000 of BASF, AG , Germany), 2.0 parts of SiO2 particles with a mean particle diameter of 3.7 micron, and with 0.25 parts of diisooctylsulfosuccinate commercially available through American Cyanamid Co under tradename AEROSOL OT 75. Water was added to give 1000 parts.
• MOWIOL 8-88 a tradename for polyvinylalcohol with a degree of hydrolysis of 88 mol. % and a molecular weight of 49000 (Mw)
• Mw molecular weight of 49000
• a recording medium with an ink-receiving layer was prepared as described for element 1, except for the fact that coating composition E was used instead of coating composition A, and the total dry coating thickness was set to 5.7 micron.
• polyvinylpyrrolidone (LUVISKOL K90, a tradename for polyvinylpyrrolidone with MW 630,000 of BASF, AG, Germany), 25 parts of a copolymer of methylmethacrylate and acrylic acid (90/10), 0.4 parts of starch particles with a mean diameter of 16.7 micron, and 0.25 parts of diisooctylsulfosuccinate commercially available through American Cyanamid Co under tradename AEROSOL OT 75 were used and adjusted by a 50/50 mixture of tetrahydrofurane and ethylacetate to give 1000 parts.
• LVISKOL K90 polyvinylpyrrolidone with MW 630,000 of BASF, AG, Germany
• the inks used for ink jet printing in the present invention were all from the aqueous type comprising the ingredients, as illustrated in table 1.
• the DeskJet cassettes (these are the cassettes of a commercial Hewlett-Packard DESKJET 500C (tradename) printer. it was filtered through a MILLIPORE type GS filter having pores with average diameter of 0.22 micron, placed under an inert N2 atmosphere in an ultrasonic vibrator and degassed for 5 minutes. After being filled the cassettes were left in the N2 atmosphere for 1 hour and then sealed before further use.
• ink-receiving elements Before using the ink-receiving elements they were first acclimatised for at least 2 hours at 25°C and 30%RH, and then a test image was jetted upon it, using one of the 3 ink jet compositions described above via the black cassette of a commercial Hewlett-Packard DeskJet 500C printer.
• the different combinations of ink-receiving layers and inks, together with the thickness of the ink-receiving layer and the values of a and b of formula (I) are given in table 2.
• the roughness of the surface of the ink-receiving layers was determined via measurement B

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• Ink Jet Recording Methods And Recording Media Thereof (AREA)

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Cited By (5)

Citations (3)

• 1994
  • 1994-09-29 EP EP94202817A patent/EP0704314A1/de not_active Withdrawn

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