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 unpublished European Application 92 203316.2
• An improvement in waterfastness is mostly realised by the use of ammonium mordanting polymers. These polymers interact with most typical ink jet inks resulting in a better localisation of the dye in the binder. Typical examples of such descriptions are US P 4,371,582, US P 4,575,465, US P 4,649,064, GB 2,210,071 and EP 423 829.
• a basic polymer latex comprising tertamino- or quaternary ammonium groups is described.
• 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.
• the above object(s) is (are) realized by providing an ink-jet recording element comprising a polymeric film substrate or a resin coated paper substrate and at least one ink-receiving layer coated thereon comprising at least one binder and at least one mordanting agent characterised in that said mordanting agent is a polymer containing a phosphonium moiety.
• 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 ink-jet 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 R1, R2 and R3 wich may be the same or different are C1-C8 alkyl-, cycloalkyl- or aryl-group and wherein n is an integer from 1 to 12, as described in EP 295 338 and EP 306 564.
• 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: (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 copo
• 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/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 2.0 g/m2, and preferably from 0.2 to 0.5 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, 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
• 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 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 SiO2 with a specific surface of 280 to 300 m2/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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• 1994
  • 1994-01-19 EP EP19940200124 patent/EP0609930B1/de not_active Expired - Lifetime

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