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
  • B41M5/506—Intermediate layers
• • 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
  • B41M5/5218—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
  • B41M5/5236—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

• the present invention relates to an improved ink-receiving material for ink jet printing.
• Ink-receiving materials for ink-jet printing must fulfil a number of stringent requirements. They contain an ink-receiving layer or ink-receiving layers which should fulfil the following requirements: a high ink-absorbing capacity, so that the dots will not flow out and will not be expanded more than is necessary to obtain a high optical density; a high ink absorbing speed (short ink drying time) so that the ink droplets will not feather if smeared immediately after applying; ready wetting by the ink so that there is no "puddling", i.e. coalescence of adjacent ink dots; no "bleeding" i.e. overlap with neighbouring or later placed dots; and no surface cracking. Furthermore, the ink-receiving material should not exhibit curl or sticky behaviour upon stacking prior to printing; and should be able to be transported through different types of printer.
• the ink-receiving material After printing the image on the ink-receiving material must exhibit good water-fastness, light-fastness, and good stability under severe conditions of temperature and humidity; and the print must not exhibit any curl or sticky behaviour upon stacked and should be able to move smoothly through different types of printers. Furthermore, transparent ink-receiving materials must have a low haze-value and be excellent in transmittance properties. It is difficult to fulfil all these requirements at the same time.
• US 3,889,270 discloses in a process for information recording comprising producing a fine jet of colored liquid, directing the jet of colored liquid onto a recording medium, modulating the density of the applied jet by an electric field in accordance with the information to be recorded, the improvement comprising the recording medium consisting of a support with an image-receiving layer, wherein the image-receiving layer is a molecular or colloidal disperse substance, which is wetted by the colored liquid and into which the colored liquid penetrates to a depth in the order of a few microns; and further discloses that the image receiving layer preferably comprises a protein, a polysaccharide, cellulose, a cellulose derivative, a polyvinyl alcohol, a copolymer of vinyl alcohols or a hydrophilic silica gel.
• US 4,440,827 discloses a process for producing a recording paper for ink jet recording and optical bar code printing having, on the surface of a support, a coating layer comprising an inorganic pigment and an aqueous polymeric binder characterized by obtaining said coating layer by twice or more repeating a coating step with the same coating color which comprises coating a coating color prepared by mixing 100 parts by weight of said inorganic pigment containing 50-100 parts by weight of synthetic silica with 5-18 parts by weight of said aqueous polymeric binder in an amount of 2-9 g solid/m 2 per one side of the support by one run of coating procedure and then drying the coating color.
• EP-A 0 379 964 discloses a recording sheet for ink jet printers which print with an aqueous ink containing a water soluble dye consisting of a carrier of a material capable of ink absorption which is coated or impregnated with an ink receptive material which contains a mixture of an amorphous silicon dioxide and a cationic resin and further disclose that that the amorphous silicon dioxide is preferably one obtained by hydrolysis of silicon tetrachloride in an oxyhydrogen flame, which consists of aggregates of ball-shaped particles with an average particle size of 7-40 nm; and that the cationic resin preferably is selected from the group consisting of polyethylene imines, polydimethyldiallyl ammonium salts, particularly chlorides, polyalkylene polyaminedicyanodiamido ammonium chlorides, polyalkylenepolyaminedicyanodiamido ammonium condensates, polyvinylpyridine halides, polymers of (meth)acrylamidoalkyl
• EP-A 1 211 086 discloses a method for the preparation of an ink jet recording element comprising coating on top of a support a layer pack comprising, in order, (a) a layer containing a pigment at a solid weight % of 60 to 98 of the total solid weight of the layer, and (b) a layer containing a water-soluble polymer, characterized in that said layers (a) and (b) are coated simultaneously wet on wet; and further discloses that the preferred pigment is an inorganic pigment, preferably silica, and that the preferred polymer is a cationic polymer, is a nitrogen containing cationic polymer, preferably a nitrogen containing cationic polymer, which is preferably is copoly(vinylalcohol-vinylacetate-diallyldimethylammonium chloride).
• EP-A 1 211 086 further discloses the use of hardening agents in the ink-receiving layers, which can be used individually or in combination and in free or in blocked form with the following hardeners being discloses: 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
• 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.
• EP-A 0 634 286 discloses a recording sheet comprising a substrate and a alumina hydrate layer formed thereon, wherein the alumina hydrate layer contains a polyvinyl alcohol in an amount of from 5 to 50 wt% relative to the alumina hydrate, and boric acid or borate in an amount of from 0.1 to 10wt% as calculated as H 3 BO 3 relative to the polyvinyl alcohol.
• JN 05-104848 discloses an ink-jet recording paper formed by successively providing a borax or boric acid treatment layer and an ink-jet recording layer of 5 to 25 g/m 2 to the gloss surface of single-sided gloss paper, the ink-jet recording layer being formed from at least 100 parts by weight of pigment based on synthetic silica and 10 to 50 parts by weight of polyvinyl alcohol.
• EP-A 0 493 100 discloses an ink jet recording paper comprising a substrate and an ink-jet recording layer formed thereon, characterized in that the substrate is coated with at least 0.1 g/m 2 of borax or boric acid on at least one face thereof, and in that the ink-jet recording layer is formed on the or one of the coated faces of the substrate at a coverage of 5-20 g/m 2 and comprises 100 parts by weight of a pigment having a synthetic silica as the main ingredient and 10-35 parts by weight of a binder having polyvinyl alcohol as the main ingredient.
• US 2002/045032A discloses a process for manufacturing a recording medium for ink-jet recording, the process comprising the steps of: 1) supplying continuously at least inorganic particles and an aqueous medium to a disperser; 2) dispersing the inorganic particles in the disperser to obtain an inorganic particle dispersion solution; 3) ejecting continuously the dispersion solution from the disperser, wherein the supplying, dispersing, and ejecting are carried at the first dispersion stage; 4) providing a coating solution containing the resulting inorganic particle dispersion solution; and 5) coating the coating solution on a support.
• EP 1 251 013A discloses an inkjet recording sheet comprising a support and, on a surface of the support, a colorant-receiving layer formed by: applying a first coating liquid, which has a pH value of at most 5 and is obtained by adding a solution that includes polyvinyl alcohol, a high boiling point organic solvent and at least one of a first nonionic surfactant and an amphoteric surfactant, to a dispersion that includes vapor-phase-process silica having a specific surface area of at least 200 m 2 /g as measured by the BET method and a cationic resin, to form a coat layer; adding, to the coat layer formed by the application of the first coating liquid, a second coating liquid, which has a pH value of at least 8.5 or higher and includes a cross-linking agent capable of cross-linking the polyvinyl alcohol, an organic mordant and a second nonionic surfactant, either at the same time as the application of the first coating liquid or during drying of the coat
• EP 1 264 705A discloses a porous resin film comprising a thermoplastic resin, an inorganic and/or organic finely divided powder and a hydrophilicizer, wherein said porous resin film has a liquid absorption capacity in accordance with "Japan TAPPI No. 51-87" of 0.5 mI/m 2 or above and the ink-receiving layer has a surface glossinesss (JIS-Z8741: measuring method at 60°) of 40%$ or above.
• US 2003/072925A discloses an ink-jet recording material which comprises a support and at least two ink-receptive layers containing inorganic fine particles and a hydrophilic binder provided by coating thereon, wherein an ink-receptive layer (A) nearer to the support contains fumed silica, and an ink-receptive layer (B) apart from the support contains alumina or alumina hydrate.
• US 2001/004487A discloses an ink-jet recording material comprising a support, a layer containing at least one of a polymer latex and a resin emulsion, and solid fine particles provided on the support, and at least one layer containing fumed silica provided on the above-mentioned layer.
• ink-receiving layers comprising aluminium oxide hydrate, e.g. boehmite or pseudo-boehmite, a boric acid or borate-hardenable binder and boric acid or a borate
• polyvinyl alcohol, hydrolyzed polyvinyl acetate i.e. a copolymer of vinyl acetate and vinyl alcohol
• copoly(vinylalcohol-vinylacetate-diallyldimethylammonium chloride) was used as the binder.
• the potlife of a dispersion containing boric acid or borate was surprisingly critically dependent upon whether polyvinyl alcohol or an at least partially hydrolyzed copolymer comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units was used.
• the hardening kinetics and hence the homogeneity of the hardening was surprisingly also critically dependent on whether polyvinyl alcohol or a hydrolyzed copolymer comprising vinyl ester and ethylenically unsaturated cationic monomer units was used.
• the ink-receiving layers obtained with at least partially hydrolyzed copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units were much more transparent than those obtained with high molecular weight polyvinyl alcohol.
• an ink-receiving material comprising a support coated on at least one side with an ink-receiving layer, the ink-receiving layer containing sub-micron silica and an at least partially hydrolyzed copolymer comprising vinyl ester and ethylenically unsaturated cationic monomer units hardened with boric acid or a borate, characterized in that said ethylenically unsaturated cationic monomer units is a quaternary ammonium salt or a quaternary phosphonium salt and said quaternary ammonium salt is an N,N-dialkenyl-N,N-dialkyl-ammonium salt.
• aspects of the present invention are also realized by a process for the preparation of an ink-receiving material comprising the steps of: coating a support on at least one side with a dispersion containing sub-micron silica particles, an at least partially hydrolyzed copolymer comprising vinyl ester monomer units, ethylenically unsaturated cationic monomer units and boric acid or a borate, thereby preparing an ink-receiving layer hardened with boric acid or a borate, characterized in that said ethylenically unsaturated cationic monomer units is a quaternary ammonium salt or a quaternary phosphonium salt and said quaternary ammonium salt is an N,N-dialkenyl-N,N-dialkyl-ammonium salt.
• Polyvinyl alcohol as used in disclosing the present invention, means a partially or fully hydrolyzed polyvinyl ester e.g. polyvinyl acetate.
• sub-micron silica particles means silica particle with an average particle size of less than 1 ⁇ m.
• an at least partially hydrolyzed copolymer comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units includes copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units which have been at least partially hydolyzed and copolymers of vinyl ester monomer units and vinyl precursor monomer units which have been at least partially hydrolyzed follows by functionalizing the precursor monomer units into ethylenically unsaturated cationic monomer units.
• ink-pervious means pervious to ink i.e. that ink can diffuse through.
• the lower limit of the ratio by weight of the total binder to the total pigment in the ink-receiving layer is 1:50.
• the lower limit of the ratio by weight of the total binder to the total pigment in the ink-receiving layer is 1:20.
• the upper limit of the ratio by weight of the total binder to the total pigment in the ink-receiving layer is 1:2.
• the upper limit of the ratio by weight of the total binder to the total pigment in the ink-receiving layer is 1:1.
• the amount of the pigment exceeds the upper limit, the strength of the ink receiving layer itself is lowered, and the resulting image hence tends to deteriorate in rub-off resistance and the like.
• the binder to pigment ratio is too great, the ink-absorbing capacity of the resulting ink-receiving layer is reduced, and so the image formed may possibly be deteriorated.
• the ink-receiving layer has a haze value of at most 45%.
• the ink-receiving layer is coated with a non-pigmented ink-pervious protective layer.
• This layer can also increase the gloss of the side or sides of the support onto which the ink-receiving layer has been coated.
• the support for use in the present invention can be selected from the paper type supports and polymeric type supports well-known from photographic technology.
• Paper types include plain paper, cast coated paper, a paper carrying a barrier layer preventing ink penetration, 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, polyvinyl chloride, polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
• PET polyethylene terephthalate
• polyethylene naphthalate polyvinyl chloride
• polyamides polycarbonates
• polyimides polyolefins
• poly(vinylacetals) polyethers and polysulfonamides.
• polyethylene terephthalate examples 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.
• a resin coated paper support is preferred.
• the support is a transparent support.
• the support is a transparent polyester support.
• the support is a resin-coated paper.
• Sub-micron silica particles as used in the ink-receiving material, according to the present invention can be amorphous or crystalline silica and can be prepared by liquid or gas phase processes e.g. spherical, non-spherical, colloidal, gel, precipitated and flame-pyrolyzed silicas.
• the silica has a primary particle size between 4 and 60 nm.
• the silica has a primary particle size between 5 and 50 nm.
• the silica has an average agglomerated particle size smaller than 500 nm.
• Particularly suitable silicas for use in the ink-receiving material, according to the present invention are: Manufacturer Specific surface area* [m 2 /g] Primary particle size [nm] HDK T30 Wacker Chemie 300 7 HDK T40 Wacker Chemie 400 5 AEROSIL® 200 Degussa 200 12 AEROSIL® 300 Degussa 300 7 AEROSIL® 380 Degussa 380 7 CAB-O-SPERSE PG0022# Cabot Corporation 200 20 (TEM) * via BET method # cationic type
• the surface charge of the aggregate particles are preferably changed from negative to positive.
• the surface charge can be changed via several methods.
• An alternative for the silica treatment of commercial available fumed silica is obtaining directly form a commercial source an aqueous dispersion of cationically modified fumed silica.
• CAB-O-SPERSE PG0022 is available from Cabot Corporation.
• Methods of preparing fine particles of cationized silica include:
• Boric acid or borate e.g. borax have the function in the ink-receiving layer of crosslinking the at least partially hydrolyzed copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units.
• the ink-receiving layer contains a further pigment.
• Suitable further pigments for incorporation into the ink-receiving layer are: kaolin, talc, clay, hydrotalcite, diatomaceous earth, calcium carbonate, barium sulphate, titanium dioxide, magnesium carbonate, basic magnesium carbonate, aluminosilicate, aluminum trihydroxide, aluminum oxide (alumina), titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, satin white, an aluminium oxide hydrate e.g. boehmite or pseudo-boehmite, zirconium oxide, silica with an average particle size greater than 1 ⁇ m or mixed oxides.
• the further pigment is selected from the group consisting of aluminosilicate, alumina, calcium carbonate, aluminium oxide hydrate, aluminum trihydroxide and mixtures thereof.
• aluminum oxide examples include ⁇ -Al 2 O 3 types, such as NORTON E700, available from Saint-Gobain Ceramics & Plastics, Inc, ⁇ -Al 2 O 3 types, such as ALUMINUM OXID C from Degussa, Other Aluminum oxide grades, such as BAIKALOX CR15 and CR30 from Baikowski Chemie; DURALOX grades and MEDIALOX grades from Baikowski Chemie, BAIKALOX CR80, CR140, CR125, B105CR from Baikowski Chemie; CAB-O-SPERSE PG003 trademark from Cabot, CATALOX GRADES and CATAPAL GRADES from Sasol, such as PLURALOX HP14/150; colloidal Al 2 O 3 types, such as ALUMINASOL 100; ALUMINASOL 200, ALUMINASOL 220, ALUMINASOL 300, and ALUMINASOL 520 trademarks from Nissan Chemical Industries or NALCO 8676 trademark from ONDEO Nalco
• a useful type of alumina hydrate is ⁇ -AlO(OH), also called boehmite, available in powder form as DISPERAL, DISPERAL HP14 and DISPERAL 40 from SASOL, MARTOXIN VPP2000-2 and GL-3 from MARTINSWERK GmbH. and as liquid boehmite alumina systems as DISPAL 23N4-20, DISPAL 14N-25, DISPERAL AL25 from SASOL.
• Useful aluminum trihydroxides include Bayerite, or ⁇ -Al(OH) 3 , such as PLURAL BT, available from SASOL, and Gibbsite, or ⁇ -Al(OH) 3 , such as MARTINAL grades from MARTINSWERK GmbH, MARTIFIN grades, such as MARTIFIN OL104, MARTIFIN OL 107 and MARTIFIN OL111 from Martinswerk GmbH , MICRAL grades, such as MICRAL 1440, MICRAL 1500; MICRAL 632; MICRAL 855; MICRAL 916; MICRAL 932; MICRAL 932CM; MICRAL 9400 from JM Huber company; HIGILITE grades, e.g.
• HIGILITE H42 or HIGILITE H43M from Showa Denka K.K.
• HYDRAL GRADES such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA, from ALCOA Industrial Chemicals.
• zirconium oxide is NALCO OOSS008 trademark of ONDEO Nalco, acetate stabilized ZrO2, ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from Nyacol Nano Technologies.
• Useful mixed oxides are SIRAL grades from SASOL, colloidal metal oxides from NALCO such as Nalco 1056, Nalco TX10496, Nalco TX11678.
• the ink-receiving layer contains an organic pigment.
• the organic pigment can be selected from the group consisting of polystyrene, polymethyl methacrylate, silicones, melamine-formaldehyde condensation polymers, urea-formaldehyde condensation polymers, polyesters and polyamides.
• Mixtures of different inorganic pigments may be used and mixtures of inorganic and organic pigments can also be used.
• the at least partially hydrolyzed copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units can be prepared by direct copolymerization and subsequent hydrolysis or by copolymerisation of a precursor for a cationic monomer with vinyl acetate, subsequent hydrolysis and then conversion of the precursor group into a cationic monomer unit.
• the N,N-dialkenyl-N,N-dialkyl ammonium salt is diallyl dimethylammonium chloride.
• the at least partially hydrolyzed copolymer comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units is a terpolymer of vinyl alcohol, vinyl acetate and diallyl dimethylammonium chloride.
• Suitable ethylenically unsaturated cationic monomer units are given below: Monomer nr M1 diallyldimethylammonium chloride M2 diallyldimethylammonium bromide M3 diallyldimethylammonium acetate M4 diallyldimethylammonium sulphonate M5 diallyldiethylammonium chloride M6 diallyldiethylammonium bromide M7 diallyldiethylammonium acetate M8 diallyldiethylammonium sulphonate M9 diallylethylmethylammonium chloride M10 diallylethylmethylammonium bromide M11 diallylethylmethylammonium acetate M12 diallylethylmethylammonium sulphonate M13 diallyl-di-n-propylammonium chloride M14 diallyl-di-n-propylammonium bromide M15 diallyl-di-
• hydrolyzed copolymers comprising vinyl ester and ethylenically unsaturated cationic monomer units, according to the present invention, may be obtained by several routes:
• the ink-receiving layer contains a further binder.
• the ink-receiving layer further contains polyvinyl alcohol.
• Suitable further binders for incorporating into the ink-receiving layer are: 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; poly(styrene), styrene copolymers; acrylic or methacrylic polymers; styrene/acrylic copolymers; ethylene-vinylacetate copolymer; vinylmethyl ether/maleic acid copolymer; poly(2-acrylamido-2-methyl propane sul
• an adhesive undercoat layer may be incorporated, on one or both sides of the support, between the support and the ink-receiving layer.
• This layer is then coated from an aqueous medium containing any of the numerous known adhesive polymers.
• Preferred adhesive polymers include styrenebutadiene latex, acrylate latices, poly(ethylene-vinylacetate), polyvinylesters, copolyesters, polyesters and polyurethanes.
• the adhesive polymers include WAC series, such as WAC-10, WAC-15, WAC-17X and WAC-20, trademarks of Takamatsu Oil & Fat Co.
• the dry coating weight of this undercoat layer when present is preferably comprised between 0.5 and 5.0 g/m 2 .
• the ink-receiving layer further contains a cationic compound acting as mordant.
• a cationic compound acting as mordant increases 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, Nalco, CIBA, Nitto Boseki Co., Clariant, BASF and EKA Chemicals.
• DADMAC copolymers such as copolymers with acrylamide, e.g. NALCO 1470 trade mark of ONDEO Nalco or PAS-J-81, trademark of Nitto Boseki Co., such as copolymers of DADMAC with acrylates, such as Nalco 8190, trademark of ONDEO Nalco; copolymers of DADMAC with SO 2 , such as PAS-A-1 or PAS-92, trademarks of Nitto Boseki Co., copolymer of DADMAC with maleic acid, e.g.
• DADMAC copolymers such as copolymers with acrylamide, e.g. NALCO 1470 trade mark of ONDEO Nalco or PAS-J-81, trademark of Nitto Boseki Co., such as copolymers of DADMAC with acrylates, such as Nalco 8190, trademark of ONDEO Nalco; copolymers of DADMAC with SO 2 , such as PAS
• PAS-410 trademark of Nitto Boseki Co., copolymer of DADMAC with diallyl(3-chloro-2-hydroxypropyl)amine hydrochloride, eg. PAS-880, trademark of Nitto Boseki Co., dimethylamine-epichlorohydrine copolymers, e.g.
• Nalco 7135 trademark of ONDEO Nalco or POLYFIX 700, trade name of Showa High Polymer Co.
• other POLYFIX grades which could be used are POLYFIX 601, POLYFIX 301, POLYFIX 301A, POLYFIX 250WS, and POLYFIX 3000 ;
• NEOFIX E-117 trade name of Nicca Chemical Co., a polyoxyalkylene polyamine dicyanodiamine, and REDIFLOC 4150, trade name of EKA Chemicals, a polyamine;
• MADQUAT methacryloxyethyl-trimethylammonium chloride
• CYPRO 514/515/516, SUPERFLOC 507/521/567 cationic acrylic polymers, such as ALCOSTAT 567, trademark of CIBA, 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; phosphonium compounds such as disclosed in EP 609930 and other cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.
• crosslinking agents are added to the ink-receiving layer and the optional backing and/or adhesive layers e.g. to provide such desired features as waterfastness and non-blocking characteristics.
• 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 otherwise known as hardening agents, can be used individually or in combination and in free or in blocked form.
• further crosslinking agents selected from the group consisting of formaldehyde, free dialdehydes, such as succinaldehyde and glutaraldehyde, blocked dialdehydes, active esters, sulfonate esters, active halogen compounds, isocyanates, blocked isocyanates, polyfunctional isocyanates, melamine derivatives, s-triazines, diazines, epoxides, active olefins having two or more active bonds, carbodiimides, zirconium complexes, e.g.
• BACOTE 20 ZIRMEL 1000 or zirconium acetate, trademarks of MEL Chemicals, titanium complexes, such as TYZOR grades from DuPont, isoxazolium salts substituted 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, copoly(acroleinmethacrylic acid), oxazoline functional polymers, e.g. EPOCROS WS-500, and EPOCROS K-1000 series, and maleic anhydride copolymers, e.g. GANTREZ AN119.
• the ink receiving layer and optional extra layers further contain(s) at least one stabilizer e.g. against light and oxidation.
• Such stabilizers include 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.
• Stilbene compounds are a preferred type of UV-absorber.
• the ink receiving layer and optional extra layers further contain(s) at least one plasticizer e.g. 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 butyl carbitol.
• plasticizer e.g. ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic
• the ink receiving layer and the optional supplementary layers further contains a surfactant.
• the ink receiving layer and the optional supplementary layers further contains a whitening agent.
• the ink receiving layer and the optional supplementary layers further contain a matting agent.
• Surfactants may be incorporated in the layers of the recording element 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, alkylallylether
• 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.
• Ink jet inks suitable for use with the ink-jet receiving material according to the present invention typically include the following ingredients: dyes or pigments; water and/or organic solvents; humectants such as glycols; detergents; thickeners; polymeric binders; and preservatives. 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. Suitable ink compositions can be roughly divided in:
• ink jet printing tiny drops of ink fluid are projected directly onto an ink-receiving surface without physical contact between the printing device and the ink-receiving surface.
• the printing device stores the printing data electronically and provides a mechanism for ejecting the drops image-wise. Printing is accomplished by moving the print-head across the ink-receiving material 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 re-collected 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 re-collected.
• 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).
• the ink dots that are applied to the ink-receiving layer should be substantially round in shape and smooth at their peripheries.
• the dot diameter must be constant and accurately controlled.
• the ink-receiving layers 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.
• Coating dispersions were prepared using different at least partially hydrolyzed copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units (INVENTION EXAMPLES 1 and 2) and different polyvinyl alcohols (COMPARATIVE EXAMPLE 1 to 7).
• the coating dispersions consist of a binder, a fumed silica and boric acid.
• the binder is an at least partially hydrolyzed copolymers comprising vinyl ester and ethylenically unsaturated cationic monomer units.
• Copolymers nr 1 and 2 are copolymers of vinyl alcohol, vinyl acetate and diallyldimethylammonium chloride.
• Hydrolyzed copolymers comprising vinyl ester and ethylenically unsaturated cationic monomer units were evaluated in comparison with polyvinyl alcohols from Air Products (USA) and Kuraray together with Celvol and Poval polyvinyl alcohols (see table below).
• the silica used was CAB-O-SPERSE® PG0022 from Cabot Corporation.
• the coating dispersions were prepared as follows:
• the coating dispersions containing the at least partially hydrolyzed copolymers comprising vinyl ester monomer units and ethylenically unsaturated cationic monomer units also offer the benefit that the coating dispersion has a longer shelf-life.
• the coating dispersion must be coated directly after addition of the boric acid.
• the cationic vinylalcohol copolymer a very long pot-life (> several days) was obtained.
• a coating dispersion with silica Cabosperse PG0022, Copolymer nr 1 and boric acid (ratio 100/25/7,5 by weight) is still coatable after 5 days.
• Table 1 Invention example nr. Copolymer nr. Viscosity of coating dispersion Coating opacity Coating quality 1 1 Low transparent Crack-free 2 2 Low transparent Crack-free Comparative example nr. Polymer nr. 1 C1 High Opaque Crack-free 2 C2 High Opaque Cracks 3 C3 Low Opaque Cracks 4 C4 High Opaque Cracks 5 C5 High Opaque Cracks 6 C6 High Opaque Cracks 7 C7 High Opaque Cracks
• the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.

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