EP0609930B1 - Tinte empfangende Schichten - Google Patents

Tinte empfangende Schichten Download PDF

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Publication number
EP0609930B1
EP0609930B1 EP19940200124 EP94200124A EP0609930B1 EP 0609930 B1 EP0609930 B1 EP 0609930B1 EP 19940200124 EP19940200124 EP 19940200124 EP 94200124 A EP94200124 A EP 94200124A EP 0609930 B1 EP0609930 B1 EP 0609930B1
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EP
European Patent Office
Prior art keywords
ink
jet recording
recording element
receiving layer
weight
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Application number
EP19940200124
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English (en)
French (fr)
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EP0609930A1 (de
Inventor
Guido C/O Agfa-Gevaert N.V. Desje
Eric C/O Agfa-Gevaert N.V. Verschueren
Luc C/O Agfa-Gevaert N.V. Lemmens
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication of EP0609930B1 publication Critical patent/EP0609930B1/de
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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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants

Definitions

  • This invention relates to ink-jet 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).
  • Polymeric substrates are becoming more important in the manufacture of ink-receiving elements for ink-jet printing (e.g. resin coated paper, polyesterfilm, etc).
  • ink-jet recording elements on a polymeric substrate for ink-jet printing is the production of transparencies. These elements are primarily intended for use on an overhead projector. More generally, these elements can be used for all kinds of viewing means by transmitted light. Such a transparency for overhead projection can easily be created by applying liquid ink dots to the ink-receptive layer using equipment such as ink jet printers.
  • 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).
  • the ink receptive layers of the prior art have been prepared for a long time using many different materials.
  • a dimensionally stable substrate such as polyethyleneterephtalate (PET), cellulosetriacetate, or paper is used most frequently and coated with one or more polymer coatings.
  • PET polyethyleneterephtalate
  • These 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 ink-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.
  • a first binder gelatin or polyvinylalcohol (PVA)
  • PVP polyvinylpyrrolidone
  • This mixture of PVA, PVP or copolymers can also be combined with a coalesced latex of co-PVA-Polyvinyl-benzylammoniumchloride (US P 4,547,405) yielding a further improvement in waterfastness.
  • the tuning of the surface energy and polarity of the receiving layer is done by the use of special (fluoro) tensides: e.g. US P 4,578,285, US P 4,781,985 and US P 5,045,864.
  • 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-0 594 896 (prior art according to Art.54(3) EPC).
  • an ink-receiving layer comprising a hydrophilic polymer with up to 50% by weight of vinylpyridine/vinylbenzylquaternary ammonium salt copolymers is claimed.
  • the quaternary ammonium derivatives are used in combination with calciumacetate, a binder, a suitable crosslinker for the binder, and an ink composition comprising a binder and a crosslinkable dye.
  • an ink-jet recording element comprising a polymeric film substrate or a resin coated paper substrate and an ink-receiving layer coated thereon comprising at least one binder and at least one mordanting agent characterised in that said mordanting agent consists of a mixture of from 5 to 70 % by weight, of a polymer containing a phosphonium moiety, and obtained by homo- or co-polymerisation of ethylenically unsaturated monomers and from 30 to 95% by weight, of a second polymer, which is free from cationic groups and has been obtained by homo- or co-polymerisation of N-vinyl imidazole or 2-methyl-2-vinyl imidazole.
  • the present invention is based upon the discovery that phosphonium mordanting polymers have an advantage over widely known ammonium mordanting polymers if used as an additive to the binder of an image-recording element used for the ink-jet printing technique.
  • a copolymer of ethylenically unsaturated monomers containing a phosphonium moiety, co-polymerised with N-vinyl imidazole or 2-methyl-2-vinyl imidazole and optionally other co-polymerisable monomers can be used as mordanting agent in the ink-receiving layer.
  • mordanting ingredients for the ink-receiving layers according to this invention are phosphonium mordanting polymers, comprising as recurring groups wherein each of
  • the ink-receptive layers in the novel transparent ink-jet recording elements according to this invention contain at least one phosphonium mordanting polymer in at least one compatible binder which may be selected from the group consisting of:
  • the ink receiving layer coatings according to the present invention may also be :
  • 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.
  • 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 silverhalide 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-receptive layer in the novel ink-jet recording elements according to this invention may also comprise particulate material, 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 having an average particle size of 1-30 ⁇ m, preferably 3-10 ⁇ 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 disintegrate.
  • 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/m 2 and preferably in a range of 0.40 to 0.90 g/m 2 with 0.50 g/m 2 being most preferred.
  • the ink-receiving layer of the invention may contain a whitening agent.
  • TiO 2 rutile or anatase
  • Amounts of whitener present in the film element can range from 0.1 to 2.0 g/m 2 , and preferably from 0.2 to 0.5 g/m 2 , and most preferably 0.3 g/m 2 .
  • 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, dietylene 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, dietylene 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
  • the ink-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 ink-receiving layers of the present invention may be coated on one side of the support either as a single layer or may be divided into two or more distinct layers, coated from the same or different coating solutions.
  • a mordanting agent which is a polymer containing a phosphonium moiety according to the present invention.
  • said mordanting agent which is a polymer containing a phosphonium moiety is preferably comprised in the ink-receiving layer that is located as far as possible from the support.
  • the ink-jet recording elements of this invention comprise a polymeric, either opaque or transparent, support for the ink-receptive layer.
  • 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), polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
  • Other examples of useful high-quality polymeric supports for the present invention 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.
  • Useful 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/acrylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
  • the ink-jet 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 ink-jet recording elements of this invention are well known to those skilled in the art.
  • the ink compositions used in such printing processes as ink-jet printing are typically liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, etc.
  • the solvent or carrier liquid is predominantly water, although ink in which organic materials such as polyhydric alcohols are used as carrier liquid, can also be used.
  • the dyes used in such ink-jet ink compositions are typically water-soluble direct dyes or acid type dyes.
  • Such liquid ink compositions have been extensively described in the prior art (US P 4,381,946, US P 4,781,758, US P 4,994,110). The following examples are presented to illustrate this invention, but not to limit the present invention thereto.
  • 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-jet recording medium with an ink-receiving transparent layer was prepared as described in example 1, except for the fact that no phosphonium polymer was added to the coating solution.
  • An ink-jet recording medium with an ink-receiving transparent layer was prepared as described in example 1, except for the fact that coating solution B was used instead of coating solution A.
  • the pH of the coating solution was adjusted to pH 6 by the addition of a sodium hydroxyde solution.
  • Silicagel KIESELSOL 300F, a tradename of Bayer AG, Leverkusen Germany for a dispersion of SiO 2 with a specific surface of 280 to 300 m 2 /g.
  • An ink-jet recording medium with an ink-receiving transparent layer was prepared as described in example 1, except for the fact that coating solution C was used instead of coating solution A.
  • An ink-jet recording medium with an ink-receiving transparent layer was prepared as described in example 1, except for the fact that coating solution D was used instead of coating solution A.
  • An ink-jet recording medium with an ink-receiving transparent layer was prepared as described in example 1, except for the fact that coating solution E was used instead of coating solution A.
  • the ink-jet recording media were first acclimatised for at least 2 hours at 25°C and 30%RH, and then a test image was jetted upon it.
  • a Hewlett-Packard DeskJet 500C was used for the ink application. The prints on the ink-jet recording media prepared in this way were evaluated as follows:
  • examples 1 to 4 present better qualities than the ink-receiving layers according to the prior art (comparative examples 1 and 2), especially in respect of the ink absorbency.
  • 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.
  • two distinct ink-receiving layers with different coating compositions were coated by simultaneously applying to one side of the substrate a layer with coating composition F (wet coating thickness 100 ⁇ m) and a layer with coating composition G (wet coating thickness 90 ⁇ m) on a pilot coating machine with layer G being the outermost layer.
  • the coatings were chilled at 5° C for 20 sec., dried at 35° C for 280 sec. at 30 % relative humidity, so as to give a dry film coating thickness of 6.7 ⁇ m for layer F and 3.3 ⁇ m for layer G. This resulted in an ink-receiving element that comprised in both ink-receiving layers a polymer comprising phosphonium moieties.
  • Example 5 An ink-receiving layer was coated as described in Example 5, except for the fact that coating composition G, forming the outermost layer, did not contain a polymer comprising phosphonium moieties. This gave an ink-receiving recording element that contained only in the ink-receiving layer closest to the support a polymer comprising phosphonium moieties.
  • Example 5 An ink-receiving layer was coated as described in Example 5, except for the fact that coating composition F, forming the layer closest to the support, did not contain a polymer comprising phosphonium moieties. This gave an ink-jet recording element layer that contained only in the outermost ink-receiving layer a polymer comprising phosphonium moieties.
  • Example 5 An ink-receiving layer was coated as described in Example 5, except for the fact that neither coating composition G nor coating composition F did contain a polymer with a phosphonium moiety.
  • the recording media were first acclimatised for at least 2 hours at 25°C and 30%RH, and then a test image was jetted upon it.
  • a Hewlett-Packard DeskJet 500C was used for the ink application.
  • the prints on the recording media prepared in this way were evaluated in the same manner as described for examples 1 to 4 and comparative examples 1 and 2. The results are given in table 2.

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

Claims (7)

  1. Ein Tintenstrahl-Aufzeichnungselement, das ein polymeres Filmsubstrat oder ein mit Harz beschichtetes Papiersubstrat und eine darauf vergossene Tinte empfangende, wenigstens ein Bindemittel und wenigstens ein Beizmittel enthaltende Schicht enthält, dadurch gekennzeichnet, daß das Beizmittel aus einer Mischung von 5 bis 70 Gew.-% eines Polymeres, das einen Phosphoniumanteil enthält und durch Homo- oder Copolymerisation von ethylenisch ungesättigten Monomeren erhalten ist, und 30 bis 95 Gew.-% eines zweiten Polymeres, das keine kationischen Gruppen enthält und durch Homo- oder Copolymerisation von N-Vinylimidazol oder 2-Methyl-2-vinylimidazol erhalten ist, besteht.
  2. Ein Tintenstrahl-Aufzeichnungselement nach Anspruch 1, dadurch gekennzeichnet, daß das einen Phosphoniumanteil enthaltende Polymere als sich wiederholende Gruppen
    Figure imgb0003
     enthält, in der R1, R2 und R3 (gleich oder verschieden) eine C1-C8-Alkyl-, -Cycloalkyl- oder -Arylgruppe sind und in der n eine ganze Zahl zwischen 1 und 12 ist.
  3. Ein Tintenstrahl-Aufzeichnungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Tinte empfangende Schicht wenigstens ein Bindemittel aus der Gruppe bestehend aus Gelatine, Polyvinylpyrrolidon oder Polyvinylalkohol enthält.
  4. Ein Tintenstrahl-Aufzeichnungselement nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Tinte empfangende Schicht zwei verschiedene Schichten umfaßt, wobei wenigstens eine Schicht ein einen Phosphoniumanteil enthaltendes Polymeres enthält.
  5. Ein Tintenstrahl-Aufzeichnungselement nach Anspruch 4, dadurch gekennzeichnet, daß das einen Phosphoniumanteil enthaltende Polymere in der sich am weitesten vom Träger entfernt liegenden, Tinte empfangenden Schicht enthalten ist.
  6. Gebrauch eines Tintenstrahl-Aufzeichnungselements, das ein polymeres Filmsubstrat oder ein mit Harz beschichtetes Papiersubstrat und eine darauf vergossene Tinte empfangende, wenigstens ein Bindemittel und wenigstens ein Beizmittel enthaltende Schicht enthält, wobei das Beizmittel ein einen Phosphoniumanteil enthaltendes Polymeres enthält, um durch Anwendung einer Tintenstrahldrucktechnik, in der das Bild durch Aufspritzen von flüssigen Tintentropfen erstellt wird, ein Bild herzustellen.
  7. Gebrauch eines Tintenstrahl-Aufzeichnungselements nach irgendeinem der Ansprüche 1 bis 5 zur Herstellung eines Bildes durch Anwendung einer Tintenstrahldrucktechnik, in der das Bild durch Aufspritzen von flüssigen Tintentropfen erstellt wird.
EP19940200124 1993-02-01 1994-01-19 Tinte empfangende Schichten Expired - Lifetime EP0609930B1 (de)

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Application Number Priority Date Filing Date Title
EP19940200124 EP0609930B1 (de) 1993-02-01 1994-01-19 Tinte empfangende Schichten

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EP93200250 1993-02-01
EP93200250 1993-02-01
EP19940200124 EP0609930B1 (de) 1993-02-01 1994-01-19 Tinte empfangende Schichten

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EP0609930B1 true EP0609930B1 (de) 1997-04-16

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0732218A1 (de) * 1995-03-16 1996-09-18 Agfa-Gevaert N.V. Tinteempfängliche Schichten für Tintenstrahlaufzeichnungselemente
JP3943159B2 (ja) * 1995-05-31 2007-07-11 三菱製紙株式会社 インクジェット記録シート
DE19736312A1 (de) 1997-08-21 1999-02-25 Agfa Gevaert Ag Inkjet-Aufzeichnungsmaterial
US6190830B1 (en) * 1998-09-29 2001-02-20 Kodak Polychrome Graphics Llc Processless direct write printing plate having heat sensitive crosslinked vinyl polymer with organoonium group and methods of imaging and printing
US6190831B1 (en) * 1998-09-29 2001-02-20 Kodak Polychrome Graphics Llc Processless direct write printing plate having heat sensitive positively-charged polymers and methods of imaging and printing
US6410202B1 (en) * 1999-08-31 2002-06-25 Eastman Kodak Company Thermal switchable composition and imaging member containing cationic IR dye and methods of imaging and printing
GB0020273D0 (en) * 2000-08-18 2000-10-04 Avecia Ltd Chemical composition
EP1238815A3 (de) * 2001-03-06 2003-11-19 Eastman Kodak Company Tintenstrahlaufzeichnungsmedium und Zeichnungsverfahren
EP3736311B1 (de) 2019-05-07 2024-07-31 Agfa Nv Wasserfreie tintenstrahltintensätze

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63307979A (ja) * 1987-06-10 1988-12-15 Fuji Photo Film Co Ltd インクジエツト記録用シ−ト
DE3778363D1 (de) * 1987-09-11 1992-05-21 Agfa Gevaert Nv Polymerisches phosphoniumbeizmittel und photographisches element, das dieses enthaelt.

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