DE60104868T2 - Improved recording material for inkjet printing - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to an improved recording element for inkjet printing.

GENERAL STATE OF THE ART

at In the majority of applications, pressure is applied by pressure contact a colored one Printing form with a printing ink receiving material in which it usually is plain paper. The most used mechanical printing technique is known as lithographic printing, the selective attraction of oleophilic color on a suitable Receiving material based.

In recently, But so-called stop-free printing systems have the conventional time Pressure contact pressure displaced to some extent for specific applications. An overview can be found e.g. in the book "Principles of Non Impact Printing "by Jerome L. Johnson (1986), Palatino Press, Irvine, CA 92715, USA.

When Non-impact printing technology has become inkjet printing due to the Simplicity of construction, practical operation and cheapest Buying into a popular one Technology enforced. Especially with limited editions of a printed matter Inkjet printing has become a preferred technology. One recent review of the Advances and trends in inkjet printing technology are being made by Hue P. Le in "Journal of Imaging Science and Technology ", Vol. 42 (1), January / February 1998, given.

In ink jet printing, tiny drops of liquid ink are injected directly onto a printing ink receiving surface and the printing device and receiving element do not physically contact each other. The printer electronically stores the print data and controls a mechanism for imagewise ejecting the drops. When printing, the printhead moves across the paper or vice versa. Too early patents on inkjet printers count US 3,739,393 . US 3,805,273 and US Pat. No. 3,891,121 ,

The Spraying the ink droplets can be done in different ways. For a first type of Injection process, the generation of a continuous droplet stream according to a pressure wave pattern. This method is known as a high pressure process. In a first embodiment, the droplet stream becomes in droplets, electrostatically charged, deflected and collected again, and in droplets, remain uncharged, continue to fly in a straight line and create the image, dissolved. In another embodiment The charged deflected droplet stream forms the picture and becomes the uncharged, undeflected stream of droplets collected again. In this variant of high-pressure ink jet method are various Distracted beams at different angles and draw like that the picture on (multiple deflection system).

To a second method the ink droplets are generated "on demand" ("DOD" method or "drop on demand" method), wherein the printing device the droplets only emits when she to serve for imaging on a printing ink receiving material. This adds complexity charging the drops, distracting hardware and resampling the ink avoided. Drop-on-demand can be ink drop generation by a mechanical movement of a piezoelectric Transducer generated pressure wave (the so-called piezoelectric method) or by discrete heat shocks (the so-called "bubble Jet "method or" Thermal Jet "method) become.

• – wässrige Tintenzusammensetzungen: der Trocknungsmechanismus umfasst Absorption, Durchdringung und Verdampfung,
• – ölige Tintenzusammensetzungen: der Trocknungsmechanismus umfasst Absorption und Durchdringung,
• – Tintenzusammensetzungen auf Lösungsmittelbasis: die Trocknung beruht hauptsächlich auf Verdampfung,
• – Heißschmelz- oder Phasenwechseltintenzusammensetzungen: das Bindemittel der Tinte ist flüssig bei Ausstoßtemperatur, aber fest bei Zimmertemperatur, keine Trocknung aber Erstarrung,
• – UV-härtbare Tintenzusammensetzungen: keine Trocknung aber Polymerisation.

Inkjet printing ink compositions typically contain the following ingredients: dyes or pigments, water and / or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders, preservatives, etc. It will be understood that the optimum composition of such an ink is applied ink jet printing method and depends on the nature of the substrate to be printed. Ink compositions can be roughly divided into the following categories:

• Aqueous ink compositions: the drying mechanism includes absorption, permeation and evaporation,
• Oily ink compositions: the drying mechanism includes absorption and permeation,
• Solvent-based ink compositions: the drying is mainly based on evaporation,
• Hot melt or phase change ink compositions: the binder of the ink is liquid at ejection temperature but solid at room temperature, no drying but solidification,
• UV-curable ink compositions: no drying but polymerization.

• – die Drucktinte aufnehmende Schicht soll ein hohes Drucktinte absorbierendes Vermögen aufweisen, so dass die Punkte nicht ausfließen und sich nicht mehr als notwendig ausbreiten werden, um eine hohe optische Dichte zu erhalten,
• – die Drucktinte aufnehmende Schicht soll eine hohe Drucktinte absorbierende Geschwindigkeit (kurze Tintentrocknungszeit) aufweisen, so dass die Tintentröpfchen nicht auslaufen werden, wenn sie sofort nach Aufspritzen verschmiert werden,
• – die auf die Drucktinte aufnehmende Schicht aufgetragenen Tintenpunkte sollen eine wesentlich runde Form aufweisen und eben am Umfang sein. Der Punktdurchmesser muss konstant und genau gesteuert werden,
• – die Drucktinte aufnehmende Schicht muss schnell angefeuchtet werden, um "Puddeln" zu vermeiden, d.h. so dass angrenzende Tintenpunkte nicht ineinander fließen können, und ein eher absorbierter Tintentropfen darf durchaus nicht "bluten", d.h. benachbarte oder später angebrachte Punkte überlappen,
• – durchsichtige Tintenstrahl-Aufzeichnungselemente müssen einerseits einen niedrigen Trübungswert und andererseits hervorragende Durchlässigkeitseigenschaften aufweisen,
• – das gedruckte Bild muss unter strengen Bedingungen von Temperatur und Feuchtigkeit mit einer guten Wasserbeständigkeit, Lichtbeständigkeit und Dauerhaftigkeit aufwarten,
• – sowohl vor als nach dem Drucken darf das Tintenstrahl-Aufzeichnungselement beim Stapeln weder Kräuseln aufweisen noch klebrig sein,
• – das Tintenstrahl-Aufzeichnungselement muss zügig durch verschiedene Typen von Druckern laufen können.

As is known, various stringent requirements are imposed on the printing ink-receiving layers used in ink-jet recording elements:

• The ink receiving layer should have a high ink absorbing capacity so that the dots will not flow out and will not propagate more than necessary to obtain a high optical density,
• The ink receiving layer should have a high ink absorbing speed (short ink drying time) so that the ink droplets will not leak if smeared immediately after spraying,
• - The ink dots applied to the printing ink layer should have a substantially round shape and be just on the circumference. The point diameter must be constantly and accurately controlled
• - the ink-receiving layer must be moistened quickly to avoid "puddling", ie, adjacent ink dots can not flow into each other, and a more-absorbed ink drop must not "bleed", ie adjacent or later attached dots overlap,
• Transparent ink jet recording elements must have a low haze value on the one hand and excellent permeability properties on the other hand;
• The printed image must have good water resistance, lightfastness and durability under severe conditions of temperature and humidity,
• Both before and after printing, the ink jet recording element should not be curled or sticky when stacked,
• - The inkjet recording element must be able to run quickly through different types of printers.

Often have to compromises are made in achieving all of these characteristics. It is difficult, at the same time, to live up to all the above conditions to become.

The presence of absorptive pigments such as silica, kaolin, talc, alumina, boehmite, etc. in the ink-receiving layer is known to provide an improvement in absorbency, color density and drying time. This effect is described in many patent applications for many different binder-based systems. US Pat. No. 3,357,846 discloses the use of pigments such as kaolin, talc, barite and TiO ₂ in starch and PVA. U.S. Patent 3,889,270 describes the use of silica in gelatin, PVA and cellulose. Pigments and particles are also in patent applications such as in DE 2,925,769 , GB 2 050 866, US-P 4 474 850, US-P 4 547 405, US-P 4 578 285, WO 88 06532, US-P 4 849 286, EP 339 604 . EP 400 681 . EP 407 881 . EP 411 638 and U.S. Patent No. 5,045,864 (non-exhaustive list).

These particulate Fabrics are available in various types of binders, of which the most common Types are gelatin, polyvinyl alcohol and polyvinylpyrrolidone, and dispersed in various types of cellulose derivatives. These usual Binders have been mentioned in numerous patents.

In EP 732 219 discloses a two-layered ink-jet printing medium comprising a liquid-absorbent base material, an ink-receiving layer provided on the base material comprising a pigment, a binder and a cationic substance, and a surface layer provided on the ink-receiving layer and containing ultrafine cationic particles. Embodiments of this teaching have improved gloss and high optical density after printing. However, this medium requires further improvements in water resistance, bleed and color palette. The present invention expands knowledge of two-layered ink-jet recording materials having improved properties.

SHORT PRESENTATION THE PRESENT INVENTION

• einen Träger und auf zumindest einer Seite des Trägers,
• (1) eine erste tintenaufnehmende Schicht, die ein Bindemittel, ein tintenabsorbierendes Hauptpigment und Pseudo-Böhmit in einer Menge zwischen 1 und 30 Gew.-%, bezogen auf das Hauptpigment, enthält, und
• (2) eine zweite tintenaufnehmende Schicht mit einem Trübungswert von höchstens 45%, die ein Bindemittel und eine kationische Substanz, die aus Teilchen mit einer mittleren Teilchengröße der agglomerierten Teilchen von weniger als 500 nm besteht, enthält.

In the present invention, there is provided an ink-jet recording element comprising, in order, the following elements:

• a carrier and on at least one side of the carrier,
• (1) a first ink-receiving layer containing a binder, a main ink-absorbing pigment and pseudo-boehmite in an amount of from 1 to 30% by weight based on the main pigment, and
• (2) a second ink-receiving layer having a haze value of at most 45% which is a binder and a cationic substance consisting of particles having an average particle size of the agglomerated particles of less than 500 nm.

In a preferred embodiment is used as the main pigment silicic acid, Aluminum silicate, alumina, calcium carbonate, aluminum hydroxide and Aluminum trihydroxide used. Very particularly preferred aluminum-containing pigments.

In The second ink-receiving layer is used as a cationic substance boehmite, cationized silica or a mixture thereof is preferable.

Both ink-receptive layers can on only one side of the carrier or on both sides of the carrier be attached. In the latter case, the corresponding layers have the same or a different composition.

In an alternative embodiment can on the second side of the carrier one or more backing layers with a different one for defining the ink-receiving layers Composition are applied.

The The recording element may further comprise at least one underlying adhesive layer contain.

current embodiments the ink-jet recording media of the invention have improved water resistance, better drying time and thus reduced bleeding, better properties in relation on the color palette and decreased coalescence.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The Composition and function of the various layers of the ink-jet recording material according to the invention will be described below with reference to the preferred embodiments of the recording material explained.

When carrier for use in the present invention, one from the photographic Technology known paper carrier or a polymeric carrier be used. As a paper carrier are plain paper, cast-coated Paper, a paper carrier with a penetration of the printing ink preventing barrier layer, polyethylene coated To name paper and polypropylene-coated paper. To polymeric carriers counting Cellulose acetate propionate or cellulose acetate butyrate, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyvinyl chloride, Polyamides, polycarbonates, polyimides, polyolefins, poly (vinyl acetals), Polyethers and polysulfonamides. Further examples of usable according to the invention high quality polymeric carrier are u.a. opaque white Polyesters and extrusion blends of polyethylene terephthalate and Polypropylene. Polyester film support and especially polyethylene terephthalate supports are known for their excellent performance Dimensional stability properties for translucent materials prefers.

For the practice In the present invention, a resin-coated paper support is preferred.

In In the present invention, the carrier is one having at least two ink-receiving layers of coated support, as the first and second ink receptive layer and sequentially as follows be described in more detail. The first layer is preferably a fairly thick layer and can be considered the ink-receiving bulk layer to be viewed as.

It is an essential feature of the present invention that the first ink-receiving layer except a binder and a absorbing main pigment pseudo-boehmite in an amount between 1 and 30 wt .-%, based on the main pigment contains.

Suitable binders are various compounds well known to those skilled in the art, including hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, methylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, water-soluble ethylhydroxyethylcellulose, cellulose sulfate, polyvinyl alcohol, vinyl alcohol copolymers, polyvinyl acetal, polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, acrylamide / acrylic acid. Copolymer, polystyrene, styrene copolymers, acrylic or methacrylic acid polymers, stryol / acrylic acid copolymers, ethylene / vinyl acetate copolymer, vinylmethyl ether / maleic acid copolymer, poly (2-acrylamide-2-methylpropanesulfonic acid), poly (diethylenetriamine-co-adipic acid), Polyvinylpyridine, polyvinylimidazole, quaternized Polyimidazoline, modified polyethyleneimine-epichlorohydrin, ethoxylated polyethylenimine, poly (N, N-dimethyl-3,5-dimethylenepiperidinium chloride), polyethylene oxide, polyurethane, melamine resins, gelatin, carrageenan, dextran, gum arabic, casein, pectin, albumin, starch, collagen derivatives, Collodion and agar-agar.

• 1) Copolymerisation von Vinylacetat mit einem kationischen Monomer und anschließende Hydrolyse. Bevorzugte kationische Monomere sind quaternäre Ammoniumsalze oder Phosponiumsalze wie Methacryloxyethyltrimethylammoniumchlorid, Diallyldimethylammoniumchlorid usw. Beispiele für solche Copolymerisationen sind in folgendem Dokument beschrieben: – „Funktional modification of poly(vinyl alcohol) by copolymerization. III. Modification with cationic monomers", Moritani Tohei, Yamauchi Junnosuke. Technical Research Center, Kuraray Company, Okayama, Japan. Polymer (1998), 39(3), 559–572.
• 2) Copolymerisation einer Vorstufe für ein kationisches Monomer mit Vinylacetat und anschließende Hydrolyse. Als Vorstufen für ein kationisches Monomer sind primäre Amine, sekundäre Amine und tertiäre Amine, die durch Protonierung kationisch gemacht werden, z.B. 2-(Dimethylamin)-ethylmethacrylat, zu nennen. Weitere Vorstufen für kationische Monomere sind Vorstufen für Monomere mit einer Aminfunktion wie Vinylacetamid. Dieses Verfahren zur Herstellung von PVA mit einer Aminfunktion ist in folgenden Patentschriften beschrieben: – „Manufacture of vinyl alcohol polymers by saponification", Fujiwara Naoki, Sato Kazuaki, Matsumoto Yoichi, Nakahara Fumio. (Kuraray Co., Ltd., Japan). JP-A 2001081128, – „Amine-functional poly(vinyl alcohol) for improving properties of recycled paper", Robeson, EP 617166 , – „Preparation of cationic poly(vinyl alcohol)", Noguchi Yasunori, Kadota Takashi. (Sakamoto Yakuhin Kogyo Co., Ltd., Japan). JP-A 03281607, – „Preparation of cationic derivatives of poly(vinyl alcohol)", Stober Reinhard, Kohn Ellen, Bischoff Dietmar. (Degussa A.-G., Fed. Rep. Ger.). DE 3626662 C1 .
• 3) Derivierung von Polyvinylalkohol, wobei Polymere mit einer Aminfunktion, einer quaternären Ammoniumfunktion oder einer quaternären Phosphoniumfunktion erhalten werden, z.B. durch Veresterung, Veretherung oder Acetalierung. Nutzbare Reagenzien zu diesem Zweck sind z.B. 4-Aminbutyraldehyddimethylacetal, Aminacetaldehyd, Glycidyltrimethylammoniumchlorid usw. Beispiele für solche Modifikationen sind in folgenden Patentschriften beschrieben: – „Paper wet-strength improvement with cellulose reactive size and amine-functional poly(vinyl alcohol) and paper", von Robeson Lloyd M., Davidowich George, Pinschmidt Robert K. Jr., (Air Products and Chemicals, Inc., USA). US 5 397 436 , – „Photographic film with improved light stability", Helling Guenter, Peters Manfred. (Agfa-Gevaert AG, Deutschland). Ger. Offen. (1996), DE 4 438 004 A1 19960502, – „Photographic recording material", Helling Guenter, Dewanckele Jean-Marie. (Agfa-Gevaert AG, Deutschland). EP 627 656 ,
• 4) ein aminmodifizierter, durch Pfropfcopolymerisation von aminmodifizierten Monomeren mit Polyvinylalkohol hergestellter Polyvinylalkohol. Das Monomer mit einer Aminfunktion kann primäre, sekundäre, tertiäre oder quaternäre Amingruppen enthalten. Ein Beispiel für eine solche Pfropfcopolymerisation wird von Celanese beschrieben: – „Ink receptive coating compositions containing poly(vinyl alcohol) grafted with amine functional groups", Rabasco John Joseph, Klingenberg Eric Howard, Boylan John Richard. (Celanese International Corporation, USA). WO 01/74599, – „Graft polymers based on vinyl ester and/or alcohol polymers and ethylenically unsaturated monomers, their preparation and their use", Denzinger Walter, Ruebenacker Martin, Nilz Claudia, Lorencak Primoz, Moench Dietmar, Schuhmacher Rudolf, Stange Andreas. (BASF AG., Deutschland). DE 19526626 .

A preferred binder for the practice of the present invention is polyvinyl alcohol (PVA), a vinyl alcohol copolymer or a modified polyvinyl alcohol. Most preferably, the polyvinyl alcohol is a cationic type polyvinyl alcohol, such as Kuraray's cationic polyvinyl alcohol classes, such as POVAL C506 and POVAL C118, and Nippon Goshei. Cationic polyvinyl alcohol can also be prepared by various procedures

• 1) Copolymerization of vinyl acetate with a cationic monomer and subsequent hydrolysis. Preferred cationic monomers are quaternary ammonium salts or phosphonium salts such as methacryloxyethyltrimethylammonium chloride, diallyldimethylammonium chloride, etc. Examples of such copolymerizations are described in the following document: Functional modification of poly (vinyl alcohol) by copolymerization. III. Modification with cationic monomers, Moritani Tohei, Yamauchi Junnosuke, Technical Research Center, Kuraray Company, Okayama, Japan, Polymer (1998), 39 (3), 559-572.
• 2) Copolymerization of a precursor for a cationic monomer with vinyl acetate followed by hydrolysis. As precursors for a cationic monomer are primary amines, secondary amines and tertiary amines which are made cationic by protonation, for example 2- (dimethylamine) ethyl methacrylate. Other precursors for cationic monomers are precursors for monomers with an amine function such as vinylacetamide. This process for the preparation of PVA having an amine function is described in the following patents: "Manufacture of vinyl alcohol polymers by saponification", Fujiwara Naoki, Sato Kazuaki, Matsumoto Yoichi, Nakahara Fumio (Kuraray Co., Ltd., Japan) -A 2001081128, - "Amine-functional poly (vinyl alcohol) for improving properties of recycled paper", Robeson, EP 617166 , "Preparation of cationic poly (vinyl alcohol)", Noguchi Yasunori, Kadota Takashi (Sakamoto Yakuhin Kogyo Co., Ltd., Japan) JP-A 03281607, "Preparation of cationic poly (vinyl alcohol)" , Stober Reinhard, Kohn Ellen, Bischoff Dietmar. (Degussa A.-G., Fed. Rep. Ger.). DE 3626662 C1 ,
• 3) derivatization of polyvinyl alcohol, whereby polymers having an amine function, a quaternary ammonium function or a quaternary phosphonium function are obtained, for example by esterification, etherification or acetalation. Useful reagents for this purpose are, for example, 4-aminobutyraldehyde dimethyl acetal, amine acetaldehyde, glycidyltrimethylammonium chloride, etc. Examples of such modifications are described in the following patents: "Paper wet-strength improvement with cellulose-reactive-size and amine-functional poly (vinyl alcohol) and paper" by Robeson Lloyd M., Davidowich George, Pinschmidt Robert K. Jr., (Air Products and Chemicals, Inc., USA). US 5,397,436 , - "Photographic film with improved light stability", Helling Guenter, Peters Manfred. (Agfa-Gevaert AG, Germany) Ger. Offen. (1996), DE 4 438 004 A1 19960502, "Photographic recording material", Helling Guenter, Dewanckele Jean-Marie. (Agfa-Gevaert AG, Germany). EP 627 656 .
• 4) an amine-modified polyvinyl alcohol prepared by graft copolymerization of amine-modified monomers with polyvinyl alcohol. The monomer having an amine function may contain primary, secondary, tertiary or quaternary amine groups. An example of such a graft copolymerization is described by Celanese: "Ink receptive coating compositions containing poly (vinyl alcohol) grafted with amine functional groups", Rabasco John Joseph, Klingenberg Eric Howard, Boylan John Richard (Celanese International Corporation, USA). WO 01/74599, "Graft polymers based on vinyl esters and / or alcohol polymers and ethylenically unsaturated monomers, their preparation and their use", Denzinger Walter, Ruebenacker Martin, Nilz Claudia, Lorencak Primoz, Moench Dietmar, shoemaker Rudolf, rod Andreas , (BASF AG, Germany). DE 19526626 ,

When Home Pigment can be an inorganic, well known to those skilled in the art Pigment, such as silica, talc, clay, hydrotalcite, Kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, basic Magnesium carbonate, aluminum silicate, aluminum trihydroxide, alumina (Alumina), titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, Satin white, boehmite (Aluminum hydroxide), zirconium oxide or mixed oxides.

In a preferred embodiment is used as the main pigment silicic acid, Aluminum silicate, clay, calcium carbonate, aluminum hydroxide or Aluminum trihydroxide used.

The use of aluminum oxide (alumina) in ink-receiving layers is described in various patents, eg US 5 041 328 . US 5,182,175 . US 5,266,383 . EP 218 956 . EP 835 762 and EP 972 650 ,

Commercially available types of alumina are α-Al ₂ O ₃ types, such as NORTON E700 from Saint-Gobain Ceramics & Plastics, Inc, γ-Al ₂ O ₃ types, such as ALUMINUM OXID C from Degussa, other classes of alumina, such as BAIKALOX CR15 and CR30 from Baikowski Chemie, DURALOX classes and MEDIALOX classes from Baikowski Chemie, BAIKALOX CR80, CR140, CR125 and B105CR from Baikowski Chemie, CAB-O-SPERSE PG003, Cabot's trademarks, CATALOX classes and CATAPAL classes 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 of Nissan Chemical Industries, or NALCO 8676, trademarks of ONDEO Nalco.

Useful types of aluminum hydroxide are γ-AlO (OH), also referred to as boehmite, such as DISPERAL, DISPERAL HP14 and DISPERAL 40, MARTOXIN VPP2000-2 and GL-3 from Martinswerk GmbH., Available in powder form by Sasol, and liquid boehmite clay Systems, eg DISPAL 23N4-20, DISPAL 14N-25 and DISPERAL AL25 from Sasol. As patents over aluminum hydroxide are EP 500 021 . EP 634 286 . US 5,624,428 . EP 742 108 . US 6,238,047 . EP 622,244 . EP 810 101 etc. to name.

Useful aluminum trihydroxides include bayerite or α-Al (OH) ₃ , such as the PLURAL BT marketed by Sasol, and gibbsite or γ-Al (OH) ₃ , such as the MARTINAL classes marketed by Martinswerk GmbH, MARTIFIN classes, such as MARTIFIN OL104 MARTIFIN OL 107 and MARTIFIN OL111 from Martinswerk GmbH, MICRAL classes such as MICRAL 1440, MICRAL 1500, MICRAL 632, MICRAL 855, MICRAL 916, MICRAL 932, MICRAL 932CM and MICRAL 9400 from JM Huber Company, HIGILITE classes, eg HIGILITE H42 or HIGILITE H43M from Showa Denka KK, and HYDRAL classes such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA from Alcoa Industrial Chemicals.

Useful types of zirconia are NALCO OOSS008, trademark of ONDEO Nalco, acetate stabilized ZrO ₂ and ZR20 / 20, ZR50 / 20, ZR100 / 20 and ZRYS4, trademarks of Nyacol Nano Technologies.

usable Mixed oxides are the SIRAL classes of Sasol and colloidal metal oxides from Nalco such as Nalco 1056, Nalco TX10496 and Nalco TX11678.

The use of silica as a pigment in ink-receptive elements is described in various old and recent patents, eg U.S. 4,892,591 . US 4,902,568 . EP 373 573 . EP 423 829 . EP 487,350 . EP 493 100 . EP 514 633 etc. Various types of silica are contemplated, such as crystalline silica, amorphous silica, precipitated silica, silica gel, colloidal silica, gas phase silica, spherical and non-spherical silica, silica mixed with calcium carbonate, as described in U.S. Pat US 5,281,467 and intrinsic porosity silica as described in WO 00/02734.

The use of calcium carbonate in ink-receiving layers is described in eg DE 2,925,769 and US 5,185,213 , The use of aluminum silicate is described in, for example DE 2,925,769 ,

mixtures from different pigments are also possible.

In an alternative embodiment be the main pigment organic particles such as polystyrene, polymethylmethacrylate, Silicones, melamine-formaldehyde condensation polymers, urea-formaldehyde condensation polymers, Polyester and polyamides used. Mixtures of inorganic and organic pigments are also suitable.

As stated above, it is an essential feature of the present invention that the first ink-receiving layer further contains pseudo-boehmite in an amount between 1 and 30% by weight, based on the main pigment. Pseudo-boehmite is also known as boehmite gel and is a finely divided needle-like aluminum hydroxide. The composition of pseudo-boehmite usually corresponds to the formula Al ₂ O ₃ .1,5-2H ₂ O and is different from crystalline boehmite.

The Embedding pseudo-boehmite into the first ink-receiving layer yields the following unexpected benefits for the ink jet recording medium: improved water resistance reduced bleeding and reduced coalescence.

The lower limit of the weight ratio of the binder to the total amount of pigment in the first ink receptive Layer is preferably about 1:50, most preferably 1:20, during which upper limit is about 2: 1, most preferably 1: 1. comes the amount of pigment once over the upper limit, so does the strength of the ink-receiving Layer itself decrease and the image obtained will be a reduction the wipe resistance and more Have properties. If the binder-to-pigment ratio is too high on the other hand, the ink absorbency of the resulting ink-receptive Slight shift and the image obtained is at increased risk on damage on.

One Another essential feature of the present invention is it is that the second ink-receiving layer has a layer with a haze value from at most 45% is and a cationic substance that is made up of particles with one mean particle size of the agglomerated Contains particles of less than 500 nm.

Under the term "cationic Substance "understands in the present invention, a substance consisting of fine Particles with positively charged surfaces, causing acidic substances like acid dyes on these surfaces can adsorb. Specific examples of this are fine particles consisting of oxides of metals such as magnesium, Calcium, aluminum, zirconium, zinc, chromium, iron, copper, tin, lead and manganese.

substances with negatively charged surfaces like silica are also eligible if their negative surface charge by means of a surface treatment is made positive.

• (1) Kieselsäure, deren Oberfläche mit einer Verbindung, die einige der obenerwähnten kationischen Metalloxide oder Metallatome enthält, behandelt ist, wobei ein Beispiel für eine solche Verfahrenweise in folgenden Dokumenten beschrieben wird: – „Cationic silica dispersion for recording material". Field, Rex J., Darsillo Michael S., Fluck David J., Laufhutte, Rudiger. (Cabot Corporation, USA). WO 00/20221, – „Recording medium excellent in ink absorptivity and process for its production, and process for producing silica-alumina composite sol". Nakahara Katsumasa, Inokuma Hisao, Hirano Hachirou, Matsubara Toshiya, Wakabayashi Masako, Kon Yoshinori. (Asahi Glass Company Ltd., Japan). EP 1112962 A1 , – „Ink-receptive coating for ink-jet recording material". Chapman David Monroe. (W.R. Grace & Co.-Conn., USA). WO 00/02736,
• (2) Kieselsäure, deren Oberfläche mit einer organischen Verbindung behandelt ist, die sowohl eine Aminogruppe oder eine daraus hergestellte quaternäre Ammoniumgruppe als eine funktionelle, gegenüber einer Silanolgruppe auf der Oberfläche der Kieselsäure reaktive Gruppe, wie Aminethoxysilan oder Aminalkylglycidylether oder Isopropanolamin, enthält, wobei Beispiele für solche Verfahrensweisen beschrieben sind in: – „Ink-jet printing ink-accepting compositions comprising cationmodified silica, vinyl polymers and cationic polymers for printing fabrics using ink-jet printers with high color depth and printing fabrics coated or impregnated with the compositions". Yasuda Masahiro, Okudo Toshifumi, Hirota Yasuhide. (Kyoeisha Chemical Co., Ltd., Japan). JP-A 2000265380, – „Ink-jet-printable image-transfer medium, process for transferring image, and cloth imaged by this process". Sato Yuko, Higuma Masahiko, Shino Yoshiyuki. (Canon Kabushiki Kaisha, Japan). EP 933225 A1 , – „Adsorption of cationic surfactants on highly dispersed silica", Mikhailova I.V., Gerashchenko I.I., Institute of Surface Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine. Colloid J. (2001), 63(4), 437–440, – „Functionalization of silica particles towards cationic polyelectrolytes using vinylformamide and 1,3-divinylimidazolidin-2-one as monomers", Meyer Torsten, Rehak Petra, Jager Christian, Voigt Ina, Simon Frank, Spange Stefan. Polymer Chemistry, Institute for Chemistry, Chemnitz University of Technology, Chemnitz, Deutschland. Macromol. Symp. (2001), 163 (Tailormade Polymers), 87–96, – „Image receiving element and method of manufacturing the element", Yarmey Susan K., Steiner Michael L. (Imation Corp., USA). WO 01/05599, – „Coated paper with good printability for ink-jet printing". Hirose Mifune, Sakaki Mamoru, Katayama Masato, Higuma Masahiko, Moriya Kenichi, Nishioka Yuko. (Canon K.K., Japan), EP 732 219 A2 , – „Manufacture of porous, laminar, inorganic products", Yokoyama Masaru, Hirao Shozo, Kishimoto Takashi, Takahama Koichi. (Matsushita Electric Works, Ltd., Japan). JP-A 62176969,
• (3) Polymerisation eines kationischen Monomers oder eines Monomers mit einer Amifunktion in Gegenwart einer Kieselsäure, wie z.B. beschrieben in: – „Ink-jet printing sheet containing cationic silica", Ito Hiroshi, Sawamoto Hidetada, Hasegawa Makoto. (Oji Paper Co., Ltd., Japan). JP-A 2001293948, – „Grafting of polymers with controlled molecular weight onto carbon black and ultrafine silica surface", Tsubokawa Norio, Yoshikawa Sachio. Department of Material Science and Technology, Faculty of Engineering, Niigata University, Niigata, Japan. Recent Res. Dev. Polym. Sci. (1998), 2 (Punkt 2), 211–228, – „Cationic polymer synthesis at inorganic surfaces", Spange, S. Inst. Org. Chem. Macromol. Chem., Jena Univ., Jena, Deutschland. Vysokomol. Soedin., Ser. A Ser. B (1993), 35(11), 1873–7.

As the cationic substance, crystalline boehmite, cationized silicic acid and mixtures thereof are preferable. Information about boehmite can be found above. Examples of the fine particles of cationized silica include

• (1) Silica whose surface is treated with a compound containing some of the above-mentioned cationic metal oxides or metal atoms, an example of such a method being described in the following documents: Cationic silica dispersion for recording material., Field, Rex J., Darsillo Michael S., Fluck David J., Laufhutte, Rudiger. (Cabot Corporation, USA) WO 00/20221, - "Recording medium excellent in ink absorptivity and process for its production, and process for producing silica-alumina composite sol ". Nakahara Katsumasa, Inokuma Hisao, Hirano Hachirou, Matsubara Toshiya, Wakabayashi Masako, Kon Yoshinori. (Asahi Glass Company Ltd., Japan). EP 1112962 A1 , "Ink-receptive coating for ink-jet recording material." Chapman David Monroe (WR Grace & Co.-Conn., USA) WO 00/02736,
• (2) silica whose surface is treated with an organic compound containing both an amino group or a quaternary ammonium group prepared therefrom as a silanol group functional group on the surface of the silicic acid reactive group such as aminethoxysilane or aminalkylglycidyl ether or isopropanolamine, examples for such procedures are described in: "Ink-jet printing ink-accepting compositions for cation modified silica, vinyl polymers and cationic polymers for printing fabrics using ink-jet printers with high color depth and printing fabrics coated or impregnated with the compositions." Yasuda Masahiro, Okudo Toshifumi, Hirota Yasuhide (Kyoeisha Chemical Co., Ltd., Japan) JP-A 2000265380, - "Ink-jet-printable image-transfer medium, process for transferring image, and cloth imaged by this process". Sato Yuko, Higuma Masahiko, Shino Yoshiyuki. (Canon Kabushiki Kaisha, Japan). EP 933225 A1 , - "Adsorption of cationic surfactants on highly dispersed silica", Mikhailova IV, Gerashchenko II, Institute of Surface Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine Colloid J. (2001), 63 (4), 437-440 , "Functionalization of silica particles towards cationic polyelectrolytes using vinylformamide and 1,3-divinylimidazolidin-2-one as monomers", Meyer Torsten, Rehak Petra, Jager Christian, Voigt Ina, Simon Frank, Clasp Stefan. Polymer Chemistry, Institute for Chemistry, Chemnitz University of Technology, Chemnitz, Germany. Macromol. Symp. (2001), 163 (Tailormade Polymers), 87-96, "Image receiving element and method of manufacturing the element", Yarmey Susan K., Steiner Michael L. (Imation Corp., USA), WO 01/05599 , "Coated paper with good printability for ink-jet printing". Hirose Mifune, Sakaki Mamoru, Katayama Masato, Higuma Masahiko, Moriya Kenichi, Nishioka Yuko. (Canon KK, Japan), EP 732 219 A2 , "Manufacture of porous, laminar, inorganic products", Yokoyama Masaru, Hirao Shozo, Kishimoto Takashi, Takahama Koichi. (Matsushita Electric Works, Ltd., Japan) JP-A 62176969,
• (3) Polymerization of a cationic monomer or a monomer having an amic function in the presence of a silica, for example as described in: Ito Hiroshi, Sawamoto Hidetada, Hasegawa Makoto (Oji Paper Co., Ltd., Japan) JP-A 2001293948 "Grafting of polymers with controlled molecular weight on carbon black and ultrafine silica surface ", Tsubokawa Norio, Yoshikawa Sachio. Department of Materials Science and Technology, Faculty of Engineering, Niigata University, Niigata, Japan. Recent Res. Dev. Polym. Sci. (1998), 2 (item 2), 211-228, - "Cationic polymer synthesis at inorganic surfaces", Spange, S. Inst. Org. Chem. Macromol. Chem., Jena Univ., Jena, Germany, Vysokomol., Soedin , Ser. A Ser. B (1993), 35 (11), 1873-7.

In a particular preferred embodiment contains the upper ink-receiving layer also contains a small amount of pseudoboehmite in an amount, preferably between 0.5 and 20%, based on the cationic substance.

The Binder of the upper ink-receiving layer may be that of the lower one mentioned ink-receptive layer List selected become. The weight ratio from particle to binder in the upper layer is preferably between 1:60 and 2: 1.

The Strength the upper ink-receiving layer is preferably smaller than the strenght the first layer (bulk layer). The dry starch the upper ink-receiving layer is preferably between 10 and 40%, based on the dry thickness of the packed bed.

The Advantages of using the second ink-receiving layer and their special composition is an improved color density, an improved color palette and the absence of coalescence.

The first and second ink-receiving layers may be on one side only on both sides of the carrier be applied. In the latter case, the corresponding layers be exactly the same layers on both sides or are they different Layers, as long as their composition meets the above definitions enough. For example, the first layer on one side may contain another major pigment as the first layer on the other side or the two upper ones Layers can contain a different cationic substance.

henceforth can be on one or both sides of the carrier between the carrier and the first ink-receiving layer has an additional underlying adhesive layer added become. This layer is made from an aqueous medium that is any may contain the numerous known adhesive polymers applied. Preferred adhesive polymers include Styrene butadiene latex, acrylate latices, poly (ethylene vinyl acetate), Polyvinyl esters, copolyesters, polyesters and polyurethanes. As adhesive polymers is also the WAC series, such as WAC-10, WAC-15, WAC-17X and WAC-20, Trademark of Takamatsu Oil & Fat Co., to name.

The dry layer weight of this possibly underlying layer is preferably between 0.5 and 5.0 g / m ² .

In Yet another alternative embodiment, the first and second ink-receiving layers on one side of the carrier be attached and will the other side with at least one backing layer with a different composition than that for the ink-receiving layers mentioned definitions coated. This layer serves, for example, to improve the Transporting in printers or controlling the curling of the recording medium. This backing layer (s) can (can) Binders, matting agents, surfactants, plasticizers, etc. included.

Except the The above-described essential ingredients may be in one or both ink-receiving layers a cationic acting as a mordant Substance be embedded. By using such substances The layer is better able to dye the ink drops to fix and hold. A particularly suitable compound is a poly (diallyldimethylammonium chloride) or abbreviated to a poly (DADMAC). These compounds are available through various companies, e.g. Aldrich, Nalco, CIBA, Nitto Boseki Co., Clariant, BASF and EKA Chemicals.

Other useful cationic compounds include DADMAC copolymers such as copolymers with acrylamide, eg NALCO 1470, trademark of ONDEO Nalco, or PAS-J-81, trademark of Nitto Boseki Co., copolymers of DADMAC with acrylates such as Nalco 8190, trademark of ONDEO Nalco, copolymers of DADMAC with 502, such as PAS-A-1 or PAS-92, trademark of Nitto Boseki Co., a copolymer of DADMAC with maleic acid, eg PAS-410, trademark of Nitto Boseki Co., a copolymer of DAD MAC with diallyl (3-chloro-2-hydroxypropyl) amine hydrochloride, eg PAS-880, trademark of Nitto Boseki Co., dimethylamine-epichlorohydrin copolymers, eg Nalco 7135, trademark of ONDEO Nalco, or POLYFIX 700, trademark of Showa High Polymer Co., other useful Polyfix classes such as POLYFIX 601, POLYFIX 301, POLYFIX 301A, POLYFIX 250WS and POLYFIX 3000, NEOFIX E-117, Trademark of Nicca Chemical Co. for a polyoxyalkylene polyamine dicyandiamine, REDIFLOC 4150, Trademark of EKA Chemicals for a Polyamine, polymers modified with MADAME (methacrylate dimethylamine ethyl = dimethylamine ethyl methacrylate) or MADQUAT (methacryloxyethyl trimethyl ammonium chloride), eg ROHAGIT KL280, ROHAGIT 210, ROHAGIT SL144, PLEX 4739L and PLEX 3073 from Rohm, DIAFLOC KP155 and other DIAFLOC products from Diafloc Co., BMB 1305 and other BMB products from EKA Chemicals, cationic epichlorohydrin adducts such as POLYCUP 171 and POLYCUP 172, trademarks of Hercules Co., CYPRO products, eg CYPRO 514/515/516 and SUPERFLOC 507/521/567 from Cytec Industries, cationic acrylic polymers such as ALCOSTAT 567, trademarks of CIBA, cationic cellulose derivatives such as CELQUAT L-200, H-100, SC-240C and SC-230M, trademarks of Starch & Chemical Co ., QUATRISOFT LM200, UCARE polymers such as JR125, JR400, LR400, JR30M and LR30M and the UCARE polymer LK, 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, all fixatives from Chukyo Europe, polyethyleneimine and copolymers, eg LUPASOL, trademarks of BASF AG, triethanolamine terechelate, eg TYZOR, trademarks of Du Pont Co., copolymers of vinylpyrrolidone such as VIVIPRINT 111, trademark of ISP, a methacrylamide-propyldimethylamine copolymer with dimethylamine-ethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trademark of ISP, and with vinylimidazole, eg LUVIQUAT CARE, LUVITEC 73W, LUVITEC VPI55 K18P, LUVITEC VP155 K72W, LUVIQUAT FC905, LUVIQUAT FC550, LUVIQUAT HM522 and SOKALAN HP56, all trademarks of BASF AG, polyamidoamines, eg RETAMINOL and NADAVIN, trademarks of Bayer AG, phosphonium compounds such as those in EP 609 930 and cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.

The ink-receiving layer and any additional Layers can also commonly known conventional Ingredients such as surfactants used as pouring additives, hardeners, plasticizers, whiteners and matting agents.

The layers of the recording element of the invention may contain any of the cationic, anionic, amphoteric and nonionic surfactants as described in JP-A 62-280068 (1987). Examples of surfactants are N-alkylamino acid salts acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, Sulfobernstein, α-olefinsulfonic, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, Alkylethersulfonsäuresalze, Alkylallylethersulfonsäuresalze, Alkylamidsulfonsäuresalze, alkylphosphoric acid salts, Alkyletherphosphorsäuresalze, Alkylallyletherphosphorsäuresalze, alkyl and alkylallyl polyoxyethylene ethers, alkylallyl-formaldehyde-fumed acid salts, alkyl allyl ether sulfonic acid salts, alkyl amide sulfonic acid salts, alkyl phosphoric acid salts, alkyl ether phosphoric acid salts, alkyl allyl phosphoric acid salts, alkyl and allyl polyoxyethylene ethers, alkylallyl formaldehyde fused polyoxyethylene ethers, block polymers with polyoxypropylene, polyoxyethylene polyoxypropyl alkyl ethers, polyoxyethylene ethers of glycol esters, polyoxyethylene ethers of sorbitan esters, polyoxyethylene ethers s of sorbitol esters, aliphatic acidic polyethylene glycol esters, glycerol esters, sorbitan esters, propylene glycol esters, sugar esters, fluoro-C ₂ -C ₁₀ -alkylcarboxylic acids, disodium N-perfluorooctanesulfonylglutamate, sodium 3- (fluoroC ₆ -C ₁₁ -alkyloxy) -1- C ₃ -C ₄ -alkylsulfonates, sodium 3- (ω-fluoro-C ₆ -C ₈ -alkanoyl-N-ethylamine) -1-propanesulfonates, N- [3- (perfluorooctanesulfonamide) -propyl] -N, N- dimethyl-N-carboxymethyleneammonium betaine, fluoro-C ₁₁ -C ₂₀ -alkylcarboxylic acids, perfluoro-C ₇ -C ₁₃ -alkylcarboxylic acids, perfluorooctanesulfonic acid-diethanolamide, Li, Kund Na-perfluoro-C ₄ -C ₁₂ -alkyl sulfonates, N-propyl N- (2-hydroxyethyl) perfluorooctane sulfonamide, perfluoro C ₆ -C ₁₀ alkylsulfonamidopropylsulfonylglycinate, bis (N-perfluorooctylsulfonyl-N-ethanolaminoethyl) phosphonate, monoperfluoroC ₆ -C ₁₆ alkylethyl phosphonates, and perfluoroalkyl betaine.

To usable cationic surfactants include N-alkyldimethylammonium chloride, Palmityltrimethylammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, an ethoxylated alkylguanidineamine complex, oleamine hydroxypropyl bistrimonium chloride, Oleylimidazoline, stearylimidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, Cocotrimonium chloride, alkyl polyglycol ether ammonium sulfate, ethoxylated Oleamine, laurylpyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyldimethylamine lactate, Coconut fatty acid amide, oleylhydroxyethylimidazoline, Isostearylethylimidonium ethosulfate, lauramidopropyl PEG-dimonium chloride phosphate, Palmityltrimethylammonium chloride and cetyltrimethylammonium bromide.

Particularly useful is for example in US-P fluorocarbon surfactant described 4,781,985 of the formula F (CF _{2) 4-9} CH ₂ CH ₂ SCH ₂ CH ₂ N ⁺ R ₃ X ^-, in which R is a hydrogen atom or an alkyl group and the fluorocarbon surfactant of the formula CF ₃ (CF ₂ ) _m CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R described in US Pat. No. 5,084,340, wherein US Pat m = 2 to 10, n = 1 to 18 and R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. These surfactants are available from DuPont and 3M. The ratio of the surfactant component in the printing ink-receiving layer is generally between 0.1 and 2 wt .-%, preferably between 0.4 and 1.5 wt .-% and is very particularly preferably 0.75 wt .-%, based on the total dry weight of the layer.

The Inventive ink receptive Layers and the possible jute layers and / or adhesive layers can be networked to desired Properties like water resistance and avoiding sticking together. By networking the layer is further rendered abrasion resistant and protected from while handling fingerprints to remain on the element. There are a variety of known, also known as curing crosslinking agents, which crosslink the film-forming binders. Hardeners can be used individually or in combination and used in free or blocked form. There is a Wide range of inventively usable Hardeners. These include 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 with two or more active bonds, carbodiimides, zirconium complexes, e.g. BACOTE 20, ZIRMEL 1000 or zirconium acetate, trademark of MEL Chemicals, titanium complexes, such as DuPont's TYZOR classes, isoxazolium salts substituted in the 3-position, esters of 2-alkoxy-N-carboxydihydroquinoline, N-carbamoylpyridinium salts, hardener with mixed function such as halogen-substituted aldehyde acids (e.g. Mucochloric and mucobromic acids), onium-substituted acroleins and vinylsulfones and polymeric hardeners such as dialdehyde and a copolymer of acrolein and methacrylic acid, polymers having an oxazoline function such as. the EPOCROS WS-500 series and the EPOCROS K-1000 series, and maleic anhydride copolymers, e.g. GANTREZ AN119.

In In the practice of the present invention, boric acid is preferred as the crosslinking agent.

The Inventive ink receptive Layers and any additional Layers can also a plasticizer such as ethylene glycol, diethylene glycol, Propylene glycol, polyethylene glycol, glycerol monomethyl ether, glycerol monochlorohydrin, Ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalicanhydride, Urea phosphate, triphenyl phosphate, glycerol monostearate, propylene glycol monostearate, Tetramethylene sulfone, N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone contain.

The Inventive ink receptive Layers and any additional Layers can also contain ingredients that the light resistance of the printed image, such as antioxidants, UV absorbers, Peroxide, extinguisher for singlet oxygen such as HALS compounds (Hindered Amine Light Stabilizers), etc. As W absorbers are preferred stilbene compounds.

The ink-receiving layers and any additional Layers can according to any conventional Coating technology such as dip coating, coating coating, Extrusion coating, spin coating, cascade coating and Curtain coating on the carrier be applied.

The The present invention will now be apparent from the following examples illustrated but not limited thereto.

EXAMPLES

example 1

• – 100 Teile des im Handel erhältlichen Aluminiumoxids CAB-O-SPERSE PG003, Warenzeichen von Cabot Co., eine 40%ige wässrige Dispersion,
• – 6,5 Teile eines Polyvinylalkohols von Nippon Goshei Co., eine 10%ige wässrige Lösung,
• – und 0,65 Teile Borsäure.

A casting composition (1-A1) is prepared containing the following ingredients:

• 100 parts of the commercially available aluminum oxide CAB-O-SPERSE PG003, trademark of Cabot Co., a 40% aqueous dispersion,
• 6.5 parts of a polyvinyl alcohol from Nippon Goshei Co., a 10% aqueous solution,
• And 0.65 parts of boric acid.

• – 100 Teile des im Handel erhältlichen Böhmits DISPERAL HP 14/2 von Sasol Co., eine 25%ige wässrige Dispersion,
• – 2 Teile eines Polyvinylalkohols von Nippon Goshei Co.,
• – und 0,2 Teile Borsäure.

A second casting composition (1-B1) is prepared containing the following ingredients:

• 100 parts of the commercially available boehmite DISPERAL HP 14/2 from Sasol Co., a 25% aqueous dispersion,
• 2 parts of a polyvinyl alcohol from Nippon Goshei Co.,
• And 0.2 parts of boric acid.

The two coating compositions are applied by cascade coating on a polyethylene-coated paper support in a double-layer wet-on-wet process, A1 in a coating weight of 35 g of alumina per m ² onto the PE layer and B1 in a layer weight of 5 g of boehmite per m ² on the aluminum oxide layer. The coatings are dried at 50 ° C. The pattern is called D1.

Six other casting compositions are prepared in the same way as 1-A1, but with the following modifications:
1-A2: A1 + 5 parts of the commercially available pseudo-boehmite DISPERAL P3, trademark of Sasol Co., a 15% aqueous dispersion,
1-A3: A1 + 10 parts DISPERAL P3,
1-A4: A1 + 15 parts DISPERAL P3,
1-A5: A1 + 20 parts DISPERAL P3,
1-A6: a casting composition of 50 parts of aluminum oxide CAB-O-SPERSE PG003, 50 parts of gas phase silica (OX 50 from Degussa), 10 parts of pseudoboehmite DISPERAL P3, 6.5 parts of a polyvinyl alcohol from Nippon Goshei Co., and 0 , 65 parts of boric acid. OX 50 and DISPERAL P3 are dispersed together in water and the silica ratio is 25%.
1-A7: a casting composition of 100 parts of silica (OX 50 ex Degussa), 20 parts of pseudo-boehmite DISPERAL P3, 6.5 parts of a polyvinyl alcohol of Nippon Goshei Co. and 0.65 part of boric acid. OX 50 and DISPERAL P3 are dispersed together in water and the silica ratio is 25%.

The casting compositions 1-A1 to 1-A7 are cascade-coated together with 1-B1 in a double-layer wet-on-wet process. The coating weight of 1-A2 to 1-AF is 35 g of alumina, alumina / silica or silica per m ² . The layer weight of the outer layer 1-B1 is 5 g boehmite per m ² . The patterns are called 1-D2 to 1-D7.

• (a) Trocknungszeit: 1 = weniger als 5 s, 2 = 5 – 10 s, 3 = 10 – 20 s, 4 = 30 s oder mehr,
• (b) Koaleszenz (Bildung großer Tropfen auf den Medien): 1 = keine Koaleszenz, 2 = Koaleszenz in sekundären Farben (200% Tinte oder mehr), 3 = Koaleszenz in primären Farben, 4 = 100%ige Koaleszenz,
• (c) Wasserbeständigkeit: 1 = keine Verschmierung der Farben, wenn über die nasse Schicht gerieben wird, 2 = leichte Verschmierung der schwarzen Farbe, 3 = Verschmierung bestimmter anderer Farben, 4 = Verschmierung aller Farben und der Schicht,
• (d) Ausbluten von gedruckten und getrockneten Farben (Ausbluten von Farbstoffen von CMYK 400% Tinte in weiße, an die Druckbereiche grenzende Striche): 1 = kein Ausbluten, 2 = mikroskopisch sichtbares Ausbluten, 3 = mit bloßem Auge wahrnehmbares Ausbluten, 4 = völliges Füllen von 1 mm-Strichen.

Materials 1-D1 through 1-D7 are printed with a test pattern on an EPSON 740, LEXMARK Z52, and HP 895 small format printer. The materials are rated qualitatively with numbers on the four following properties:

• (a) drying time: 1 = less than 5 s, 2 = 5 - 10 s, 3 = 10 - 20 s, 4 = 30 s or more,
• (b) coalescence (large drop formation on the media): 1 = no coalescence, 2 = coalescence in secondary colors (200% ink or more), 3 = coalescence in primary colors, 4 = 100% coalescence,
• (c) water resistance: 1 = no smearing of the colors when rubbing over the wet layer, 2 = slight smearing of the black color, 3 = smearing of certain other colors, 4 = smearing of all colors and the layer,
• (d) bleeding of printed and dried colors (bleeding of dyes of CMYK 400% ink into white lines adjacent to the print areas): 1 = no bleed, 2 = microscopically visible bleed, 3 = bleed perceptible to the naked eye, 4 = blank Fill 1 mm lines.

The Results are listed in Table 1 below.

TABLE 1

The Results of Table 1 clearly show the influence of the presence from pseudo-boehmite in the underlying layer on the water resistance and bleeding the print area proved. The ratio reaches an optimal Value. At the highest value (20% pseudo-boehmite) Drying time and coalescence get worse. The findings apply to all cases, in which alumina, silica or mixtures of alumina and silica used as the main pigment become.

Example 2

In This example illustrates the influence of pseudo - boehmite as an auxiliary pigment in a boehmite explained as Hauptingrediens containing topcoat.

• – 100 Teile des im Handel erhältlichen Aluminiumoxids CAB-O-SPERSE PG003, Warenzeichen von Cabot Co., eine 40%ige wässrige Dispersion,
• – 10 Teile des Pseudo-Böhmits DISPERAL P3 von Sasol, eine 15%ige wässrige Dispersion,
• – 6,5 Teile eines Polyvinylalkohols von Nippon Goshei Co., eine 10%ige wässrige Lösung,
• – und 0,65 Teile Borsäure.

A casting composition (2-A1) is prepared containing the following ingredients:

• 100 parts of the commercially available aluminum oxide CAB-O-SPERSE PG003, trademark of Cabot Co., a 40% aqueous dispersion,
• 10 parts of the pseudo-boehmite DISPERAL P3 from Sasol, a 15% aqueous dispersion,
• 6.5 parts of a polyvinyl alcohol from Nippon Goshei Co., a 10% aqueous solution,
• And 0.65 parts of boric acid.

• – 100 Teile des im Handel erhältlichen Böhmits DISPERAL HP 14/2 von Sasol Co., eine 25%ige wässrige Dispersion,
• – 2 Teile eines Polyvinylalkohols von Nippon Goshei Co.,
• – und 0,2 Teile Borsäure.

A second casting composition (2-B1, analog 1-B1) is prepared containing the following ingredients:

• 100 parts of the commercially available boehmite DISPERAL HP 14/2 from Sasol Co., a 25% aqueous dispersion,
• 2 parts of a polyvinyl alcohol from Nippon Goshei Co.,
• And 0.2 parts of boric acid.

• 2-B2 : 2-B1 + 2 Teile DISPERAL P3, Pseudo-Böhmit von Sasol, eine 15%ige wässrige Dispersion,
• 2-B3 : 2-B1 + 4 Teile DISPERAL P3,
• 2-B4 : 2-B1 + 8 Teile DISPERAL P3,
• 2-B5 : 2-B1 + 16 Teile DISPERAL P3.

Four other casting compositions 2-B2 to 2-B5 are prepared in the same way as 2-B1, but with the following modifications:

• 2-B2: 2-B1 + 2 parts DISPERAL P3, pseudo-boehmite from Sasol, a 15% aqueous dispersion,
• 2-B3: 2-B1 + 4 parts DISPERAL P3,
• 2-B4: 2-B1 + 8 parts DISPERAL P3,
• 2-B5: 2-B1 + 16 parts DISPERAL P3.

In a double-layer wet-on-wet process, five coatings 2-D1 to 2-D5 are prepared by cascade coating on a polyethylene-coated paper support, 2-A1 in a coating weight of 35 g of aluminum oxide per m ² on the PE layer and 2 B1 to 2-B5 in a layer weight of 5 g boehmite per m ² on the 2-A1 layer. The coatings are dried at 50 ° C. The patterns are called 2-D1 to 2-D5.

The five materials will be printed on a small format EPSON printer using a test pattern 740, LEXMARK Z52 and HP 895 printed. The materials are evaluated analogously to the samples of Example 1. The results are listed in Table 2 below.

TABLE 2

The Results of Table 2 clearly show that the Presence of pseudo-boehmite in increasing proportion in a bohemian Layer on a pigment / pseudo-boehmite layer a favorable Influence on the bleeding of printed and dried media Has. With a high pseudo-boehmite ratio (more than 5%) in the topcoat, the coalescence and worsen the drying time. So there is an optimal ratio of Böhmitmenge to the amount of pseudo-boehmite in the topcoat.

Example 3

In a third group of experiments will be the pseudo-boehmite in the bulk layer and replacing the topcoat with cationic organic polymers, to prove the advantage of using pseudo-boehmite.

• – 100 Teile des im Handel erhältlichen Aluminiumoxids CAB-O-SPERSE PG003, Warenzeichen von Cabot Co., eine 40%ige wässrige ¹ Dispersion,
• – 6,5 Teile eines Polyvinylalkohols von Nippon Goshei Co., eine 10%ige wässrige Lösung,
• – und 0,65 Teile Borsäure.

The following casting composition (3-A1) is prepared:

• 100 parts of the commercially available alumina CAB-O-SPERSE PG003, trademark of Cabot Co., a 40% aqueous dispersion ¹ ,
• 6.5 parts of a polyvinyl alcohol from Nippon Goshei Co., a 10% aqueous solution,
• And 0.65 parts of boric acid.

• 3-A2 : 3-A1 + 1 Teil POLYFIX 301A (von Showa High Polymer, Japan),
• 3-A3 : 3-A1 + 1 Teil POLYFIX 250 WS (von Showa High Polymer, Japan),
• 3-A4 : 3-A1 + 1 Teil NEOFIX 117 (von Nicca Chemical Co., Japan),
• 3-A5 : 3-A1 + 1 Teil CAT FLOC L (von ONDEO Nalco).

Four other casting compositions 3-A2 to 3-A5 are prepared in the same way as 3-A1, but with the following modifications:

• 3-A2: 3-A1 + 1 part POLYFIX 301A (from Showa High Polymer, Japan),
• 3-A3: 3-A1 + 1 part POLYFIX 250 WS (from Showa High Polymer, Japan),
• 3-A4: 3-A1 + 1 part NEOFIX 117 (from Nicca Chemical Co., Japan),
• 3-A5: 3-A1 + 1 part CAT FLOC L (from ONDEO Nalco).

• – 100 Teile des im Handel erhältlichen Böhmits DISPERAL HP 14/2 von Sasol Co., eine 25%ige wässrige Dispersion,
• – 2 Teile eines Polyvinylalkohols von Nippon Goshei Co.,
• – und 0,2 Teile Borsäure.

Another casting composition 3-B1 is prepared containing the following ingredients:

• 100 parts of the commercially available boehmite DISPERAL HP 14/2 from Sasol Co., a 25% aqueous dispersion,
• 2 parts of a polyvinyl alcohol from Nippon Goshei Co.,
• And 0.2 parts of boric acid.

• 3-B2 : 3-B1 + 1 Teil POLYFIX 301A (von Showa High Polymer, Japan),
• 3-B3 : 3-B1 + 1 Teil POLYFIX 250 WS (von Showa High Polymer, Japan),
• 3-B4 : 3-B1 + 1 Teil NEOFIX 117 (von Nicca Chemical Co., Japan),
• 3-B5 : 3-B1 +1 Teil CAT FLOG L (von ONDEO Nalco Co.,).

Four other casting compositions 3-B2 to 3-B5 are prepared in the same way as 3-B1, but with the following modifications:

• 3-B2: 3-B1 + 1 part POLYFIX 301A (from Showa High Polymer, Japan),
• 3-B3: 3-B1 + 1 part POLYFIX 250 WS (from Showa High Polymer, Japan),
• 3-B4: 3-B1 + 1 part NEOFIX 117 (from Nicca Chemical Co., Japan),
• 3-B5: 3-B1 +1 part CAT FLOG L (from ONDEO Nalco Co.,).

In a double-layer wet-on-wet process, cascade coating adds five layers Coatings 3-D1 to 3-D5 prepared on a polyethylene-coated paper support, 3-A1 to 3-A5 in a coating weight of 35 g of alumina per m ² on the PE layer and 3-B1 to 3-B5 in a coating weight of 5 g Boehmite per m ² on the corresponding aluminum oxide layer. The coatings are dried at 50 ° C.

The Materials 3-D1 to 3-D5 are combined with a test pattern on one Small format printers of types EPSON 740, LEXMARK Z52 and HP 895 printed. The materials are evaluated analogously to the previous examples. The results are listed in Table 3 below.

TABLE 3

The Results of Table 3 show that by using cationic Polymers in the bulk layer and the topcoat reduces bleeding, but at the same time is accompanied by an exacerbation of coalescence. Therefore the presence of pseudo-boehmite in a boehmite layer favorable to Bleeding of printed and dried media to prevent and to avoid coalescence.

To the detailed description of preferred embodiments of the present invention It should be clear to the experts in this field that here within the scope of the following claims numerous modifications possible are.

Claims (19)

An ink jet recording element, which is the Series comprising the following elements: a carrier and on at least one side of the wearer, (1) a first ink-receiving layer containing a binder, an ink-absorbing Main pigment and pseudo-boehmite in an amount between 1 and 30% by weight, based on the main pigment, contains and (2) a second ink-receiving layer having a haze value from at most 45%, which is a binder and a cationic substance made up of Particles having an average particle size of the agglomerated particles of less than 500 nm contains. An ink jet recording element according to claim 1, characterized in that cationized as kationische substance boehmite silica or a mixture thereof is used. An ink jet recording element according to claim 1 or 2, characterized in that as the main pigment in the first ink-receiving layer silica, aluminum silicate, alumina, Calcium carbonate, aluminum hydroxide, aluminum trihydroxide or a Mixture thereof is used. An ink jet recording element according to claim 1 or 2, characterized in that the main pigment in the first ink-receiving layer is an inorganic pigment. Ink jet recording element according to one of claims 1 to 4, characterized in that the second ink-receiving Layer further also contains pseudo-boehmite. Ink jet recording element according to claim 5, characterized in that the pseudo-bohemian in an amount between 0.5 and 20%, based on the cationic substance, in the second ink-receiving layer. Ink jet recording element according to one of claims 1 to 6, characterized in that the dry strength of second ink-receiving layer (2) between 10 and 40%, based on the dry strength the first ink-receiving layer (1) lies. Ink jet recording element according to one of claims 1 to 7, characterized in that the binder of the layers (1) and / or (2) is polyvinyl alcohol. An ink jet recording element according to claim 8, characterized in that the polyvinyl alcohol is a cationic Polyvinyl alcohol is. Ink jet recording element according to one of claims 1 to 9, characterized in that the layer (1) and / or the Layer (2) also a hardener contains (contain). An ink jet recording element according to claim 10, characterized in that the hardener is boric acid. Ink jet recording element according to one of claims 1 to 11, characterized in that the carrier is a translucent carrier. An ink jet recording element according to claim 12, characterized in that the translucent carrier is a polyester carrier. Ink jet recording element according to one of claims 1 to 11, characterized in that the carrier is a resin-coated carrier. Ink jet recording element according to one of claims 1 to 14, characterized in that the defined in claim 1 first ink-receiving layer and that defined in claim 1 second ink-receiving layer applied to both sides of the carrier be with the corresponding layers on both sides of the may have the same or a different composition. Ink jet recording element according to one of claims 1 to 14, characterized in that the defined in claim 1 first ink-receiving layer and that defined in claim 1 second ink-receiving layer applied to only one side of the carrier and on the other side of the carrier at least one backing layer, which is not equal to the ink-receiving layers applied becomes. An ink jet recording element according to claim 16, characterized in that the backing layer (s) a matting agent contains (contain). Ink jet recording element according to one of claims 1 to 17, characterized in that the element further on a or both sides of the carrier an additional underlying, between the carriers and the first ink-receiving layer includes an adhesive layer. An ink jet recording element according to claim 18, characterized in that the underlying adhesive layer contains an adhesive polymer latex.