DE60220520T2 - Ink jet recording material - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

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

GENERAL PRIOR ART

at In the majority of applications, pressure is applied by pressure contact a colored one Printing form with an ink-attracting material which comprises usually plain paper. The most used mechanical Printing technique is known as lithographic printing based on selective Attraction of oleophilic paint on a suitable receiving material based.

Recently, however, so-called non-impact printing systems have displaced conventional pressure contact pressure to some extent for specific applications. An overview can be found eg 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 JP 2001-080203A discloses a recording material which can hold both dye ink and pigment ink and whose structure is characterized in that a first and second ink-receiving layer containing a binder resin and a pigment are superimposed on at least one side of a translucent plastic film. In this composition, the binder resin as resin components contains 40 to 60 parts by weight of a water-soluble resin and 60 to 40 parts by weight of a hydrophilic resin, the pigment content in the first ink-receiving layer is higher than in the second ink-receiving layer, and the first ink-receiving layer has a higher film thickness than the second ink-receiving layer.

In JP 2000-043405A there is disclosed a recording medium provided on at least one surface of a base support material with an ink-receiving layer containing as an essential ingredient a copolymer resin consisting of at least one of a hydrophobic monomer, a cationically-modified acrylic monomer and diacetone acrylamide as a monomer component. By laminating the ink-image-receiving layer and a protective layer containing a copolymer resin and minute grains, an ink jet recording material excellent in image quality and ink drying ability is obtained. Moreover, by using diacetone acrylamide as the acrylic monomer in an amide system for dyeing the ink, good image quality and, in combination with a dihydrazide compound, complete water resistance can be obtained.

In EP 0 415 849A discloses a printing sheet comprising a support body and a surface layer, wherein the layer covers at least one side of the support body and a copolymer containing two kinds of acrylic monomers, ie one kind of monomers having carboxyl groups and the other kind of monomers selected from the group consisting of amino groups and Amide groups, and optionally further contains a pigment.

In inkjet printing, tiny drops of liquid ink are injected directly onto an ink-attracting surface, and the printing device and receiver 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 of the ink droplets can be done in different ways. In a first type of spraying process, the generation of a continuous stream of droplets corresponding to a pressure wave pattern occurs. This process is known as a high pressure process. In a first embodiment, the droplet stream is dissolved in droplets that are electrostatically charged, deflected, and collected again, and dissolved into droplets that remain uncharged, continue to fly in a straight line, and create the image. In another embodiment, the charged deflected droplet stream forms the image and becomes the uncharged, non-deflected droplet stream collected again. In this variant of high-pressure ink jet method, different beams are deflected at different angles and thus record the image (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 there ejects on the ink-attracting material, where an image is actually produced. 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-härtende 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 penetration,
• 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 tintenanziehende 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 tintenanziehende 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 tintenanziehende Schicht aufgetragenen Tintenpunkte sollen eine wesentlich runde Form aufweisen und eben am Umfang sein. Der Punktdurchmesser muss konstant und genau gesteuert werden,
• • die tintenanziehende Schicht muss schnell angefeuchtet werden, um Zusammenlaufen 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 Tintenstrahlaufzeichnungselemente 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 Tintenstrahlaufzeichnungselement beim Stapeln weder Kräuseln aufweisen noch klebrig sein und
• • das Tintenstrahlaufzeichnungselement muss zügig durch verschiedene Typen von Druckern laufen können.

The ink-attracting layers used in ink-jet recording materials are known to impose various stringent requirements:

• The ink-attracting 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-attracting 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 ink-attracting layer should have a substantially round shape and be just around the circumference. The point diameter must be constantly and accurately controlled
• The ink-attracting layer must be moistened quickly to prevent convergence, ie, so that 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, and
• • 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.

To the Get quick-drying high gloss images with high color densities it is desirable that the ink-absorbing layer has a relatively high coating weight as well has a high pigment / binder ratio. Disadvantage of a However, such high pigment / binder ratio is that the ink-withdrawing layer is likely to lose mechanical strength, in particular when using a flexible carrier. This is often called Visualize microcracks. Therefore very desirable are measures which allow to avoid cracking, but without the others affect good image properties.

BRIEF PRESENTATION OF THE PRESENT INVENTION

task The present invention is to provide a recording material for inkjet printing, with a crack-free finished image with high gloss and high densities is obtained.

in der R1 eine Alkylgruppe, R2 eine Alkylgruppe oder Arylgruppe, R3 ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe, L eine Verbindungseinheit aus der Gruppe bestehend aus CO-NH, CO-O und CO und R4 ein Wasserstoffatom oder eine Alkylgruppe bedeutet, und das Verhältnis des Pigments zum Bindemittel zumindest 4 beträgt.The above-mentioned favorable effects are achieved by providing a recording material for ink-jet printing with a support and at least one ink-attracting layer containing a pigment and a polymeric binder, characterized in that the polymeric binder is a structural unit derived from a monomer of the following formula (I) includes:

wherein R 1 is an alkyl group, R 2 is an alkyl group or aryl group, R 3 is a hydrogen atom, an alkyl group or an aryl group, L is a compound unit selected from the group consisting of CO-NH, CO-O and CO and R 4 is a hydrogen atom or an alkyl group, and Ratio of the pigment to the binder is at least 4.

In a preferred embodiment R1, R2 and R3 represent a methyl group, L represents a CO-NH group and R4 represents a hydrogen atom or a methyl group, i. the monomer is diacetone (meth) acrylamide.

Preferably it is the polymeric binder is a copolymer from the monomer of formula (I) and other types of monomers. Most preferably, the polymeric binder is a copolymer from vinyl alcohol, vinyl acetate and diacetone acrylamide.

Further Advantages and embodiments The present invention will become apparent from the following description seen.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The various layers and ingredients of the ink-receptive invention Media will now be explained in detail below.

- Carrier

When carrier for use in the present invention are from the photographic To call technology well-known paper carriers and polymeric carriers. Suitable paper types are i.a. Plain paper, cast-coated paper, polyethylene coated paper and polypropylene coated paper. Suitable polymeric carriers are u.a. carrier from cellulose acetate propionate or cellulose acetate butyrate, polyesters such as Polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, Polyimides, polyolefins, poly (vinyl acetals), polyethers and polysulfonamides. Further examples of According to the invention usable high quality polymeric carriers are u.a. opaque carrier from white Polyesters and extrusion blends of polyethylene terephthalate and Polypropylene. Due to their excellent shape retention properties become polyester film carriers and especially polyethylene terephthalate carriers are preferred. Using such a polyester support as a carrier material An adhesive layer may be used to reduce the adhesion of the ink-receptive Layer on the carrier to improve. For Adhesive layers useful for this purpose are well known in the art photographic area. As examples, u.a. Polymers of vinylidene chloride such as Terpolymers of vinylidene chloride, acrylonitrile and acrylic acid or Terpolymers of vinylidene chloride, methyl acrylate and itaconic acid to mention.

- Ink-receptive layer

The essential feature of the present invention is that the porous one ink-receiving layer except also a polymeric binder with one of a pigment Monomer of formula (I) derived structural unit contains.

4-Methyl-1-octen-3,6-dion, CASRN 172946-87-1:

Diacetonmethacrylamid, CASRN 22029-67-0:

2-Methyl-2-propensäure-1,1-dimethyl-3-oxobutylester, CASRN 93940-09-1:

3-Oxo-1,1-dimethylbutylacrylat, CASRN155844-84-1:

N-(1-Methyl-1-ethyl-3-oxopentyl)-acrylamid, CASRN10193-02-9:

Diacetophenonacrylamid, CASRN20282-44-4:

N-(1-Isopropyl-1,5-dimethyl-3-oxohexyl)-acrylamid, CASRN40660-71-7:

N-[1,5-Dimethyl-1-(2-methyl-1-propyl)-3-oxohexyl]-acrylamid, CASRN10193-03-0:

N-(1,3-Dicyclohexyl-1-methyl-3-oxopropyl)-acrylamid, CASRN40660-70-6:

Useful monomers for use in the present invention are listed in the list below. Diacetone acrylamide, CASRN. 2873-97-4:

4-methyl-1-octene-3,6-dione, CASRN 172946-87-1:

Diacetone methacrylamide, CASRN 22029-67-0:

2-Methyl-2-propenoic acid 1,1-dimethyl-3-oxobutyl ester, CASRN 93940-09-1:

3-Oxo-1,1-dimethylbutyl acrylate, CASRN155844-84-1:

N- (1-methyl-1-ethyl-3-oxopentyl) -acrylamide, CASRN10193-02-9:

Diacetophenone acrylamide, CASRN20282-44-4:

N- (1-Isopropyl-1,5-dimethyl-3-oxohexyl) -acrylamide, CASRN40660-71-7:

N- [1,5-dimethyl-1- (2-methyl-1-propyl) -3-oxohexyl] -acrylamide, CASRN10193-03-0:

N- (1,3-dicyclohexyl-1-methyl-3-oxopropyl) -acrylamide, CASRN40660-70-6:

Such Comonomers have the advantage of being self-crosslinking, improve crosslinking by a separate crosslinking agent or over their functional group interacts with the inorganic Pigment can enter. Compared with similar ones polymeric binders, but not this functional monomer The pigmented layer clearly waits with an improved mechanical strength and less cracking. Except the improved tear resistance can Furthermore, a very high gloss and high printing densities are obtained.

The used according to the invention polymeric binder may be conventional with those skilled in the art Binders are added.

One another essential ingredient of the ink-receiving layer is a pigment.

The pigment used in the ink-receptive layer is preferred an inorganic, neutral, anionic or cationic pigment. To count usable pigments e.g. silica, Talc, clay, hydrotalcite, kaolin, diatomaceous earth, calcium carbonate, Magnesium carbonate, basic magnesium carbonate, aluminum silicate, Aluminum trihydroxide, alumina, titania, zinc oxide, Barium sulfate, calcium sulfate, zinc sulfide, satin white, aluminum hydroxide like boehmite, Zirconium oxide or mixed oxides.

Prefers is a cationic pigment selected from the group consisting of alumina hydrate, Aluminas, aluminum hydroxides, aluminum silicates and cationic modified silicas.

A preferred type of aluminum hydroxide is crystalline boehmite, also called γ-AlO (OH). Useful types of boehmite include, in powder form, DISPERAL, DISPERAL HP14 and DISPERAL 40 from Sasol, MARTOXIN VPP2000-2 and GL-3 from Martinswerk GmbH, and liquid boehmite clay systems, eg DISPAL 23N4-20, DISPAL 14N-25 and DISPERAL AL25 from Sasol. Patents on aluminum hydroxide include EP 500 021 . EP 634 286 . US 5,624,428 . EP 742 108 . US 6,238,047 . EP 622,244 . EP 810 101 etc.

Useful cationic alumina (alumina) grades include α-Al ₂ O ₃ grades such as NORTON E700 from Saint-Gobain Ceramics & Plastics Inc., γ-Al ₂ O ₃ grades such as ALUMINUM OXID C from Degussa, other alumina classes 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 ,

Other useful cationic inorganic pigments include aluminum trihydroxides such as bayerite, α-Al (OH) ₃ , such as the PLURAL BT marketed by Sasol, and gibbsite, γ-Al (OH) ₃ , such as the MARTINAL classes marketed by Martinswerk GmbH; MARTIFIN classes marketed by Martinswerk GmbH such as MARTIFIN OL 104, MARTIFIN OL 107 and MARTIFIN OL 111, MICRAL classes such as MICRAL 1440, MICRAL 1500, MICRAL 632, MICRAL 855, MICRAL 916, MICRAL 932, MICRAL 932CM and MICRAL 9400 of JM Huber Company, HIGILITE classes, eg HIGILITE H42 or HIGILITE H43M from Showa Denka KK, and HYDRAL COATES-Klasen from Alcoa Co., such as HYDRAL COAT 2, 5 and 7, HYDRAL PGA and HYDRAL 710.

Another useful type of cationic pigment is zirconia, such as NALCO OOSS008, trademark of ONDEO Nalco, and acetate stabilized ZrO ₂ and ZR20 / 20, ZR50 / 20, ZR100 / 20 and ZRYS4, trademarks of Nyacol Nano Technologies.

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

Another preferred type of inorganic pigment is silica, in its anionic base form or cationically modified form. Silica as a pigment in ink-attracting elements is described in numerous 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 possible, such as crystalline silicic acid, amorphous silica, precipitated silica, gas phase silicic acid, silica gel, spherical silicic acid and non-spherical silicic acid. The silica may contain small amounts of a metal oxide selected from the group consisting of Al, Zr and Ti. Usable types include AEROSIL OX50 (specific surface area according to the BET method: 50 + 15 m ² / g, average primary particle size 40 nm, SiO ₂ content> 99.8%, Al ₂ O ₃ content <0.08% ), AEROSIL MOX170 (BET specific surface area: 170 g / m ² , average primary particle size 15 nm, SiO ₂ content> 98.3%, Al ₂ O ₃ content 0.3-1.3%) , AEROSIL MOX80 (BET specific surface area: 80 + 20 g / m ² , mean primary particle size 30 nm, SiO ₂ content> 98.3%, Al ₂ O ₃ content 0.3-1.3% ) or other hydrophilic AEROSIL classes from Degussa-Hüls AG, with which aqueous dispersions with a small average particle size (<500 nm) can be obtained.

• (1) Oberflächenbehandlung von Kieselsäure mit einer anorganischen kationischen Verbindung wie gewissen Metalloxiden und Oxyhydroxiden, z.B. Aluminiumoxiden, und Aluminiumhydroxiden wie Böhmit und Pseudo-Böhmit/eine nutzbare kationische anorganische Verbindung zur Modifizierung von Kieselsäure ist Pseudo-Böhmit. Pseudo-Böhmit wird ebenfalls als Böhmitgel bezeichnet und ist feinteiliges nadelförmiges Aluminiumhydroxid. Die Zusammensetzung von Pseudo-Böhmit entspricht der allgemeinen Formel Al₂O₃·1,5-2H₂O und ist unterschiedlich zur Formel von kristallinem Böhmit,
• (2) Oberflächenbehandlung von Kieselsäure mit einer organischen Verbindung, die sowohl eine Aminogruppe oder eine daraus hergestellte quaternäre Ammoniumgruppe oder quaternäre Phosphoniumgruppe als eine funktionelle, gegenüber einer Silanolgruppe auf der Oberfläche der Kieselsäure reaktive Gruppe, wie Aminethoxysilan oder Aminalkylglycidylether oder Isopropanolamin, enthält, und
• (3) Polymerisation eines kationischen Monomers oder eines Monomers mit einer Aminfunktion in Gegenwart einer Kieselsäure.

Cationically modified silica may be prepared in a non-limiting manner by the following methods:

• (1) Surface treatment of silica with an inorganic cationic compound such as certain metal oxides and oxyhydroxides, eg, aluminas, and aluminum hydroxides such as boehmite and pseudo-boehmite / a useful cationic inorganic compound for modifying silica is pseudo-boehmite. Pseudo-boehmite is also referred to as boehmite gel and is finely divided needle-shaped aluminum hydroxide. The composition of pseudo-boehmite corresponds to the general formula Al ₂ O ₃ · 1.5-2H ₂ O and is different from the formula of crystalline boehmite,
• (2) surface treatment of silica with an organic compound containing both an amino group or a quaternary ammonium group or quaternary phosphonium group produced therefrom as a functional silanol group on the surface of the silica reactive group such as aminethoxysilane or aminalkylglycidyl ether or isopropanolamine;
• (3) Polymerization of a cationic monomer or a monomer having an amine function in the presence of a silicic acid.

In an alternative embodiment can as pigment organic particles such as polystyrene, polymethyl methacrylate, Silicones, melamine-formaldehyde condensation polymers, urea-formaldehyde condensation polymers, Polyester and polyamides are used. Mixtures of inorganic and organic pigments are also suitable. Most notably however, the pigment is preferably an inorganic pigment.

The Pigment is in a relationship sufficient to make the ink-attracting layer sufficiently porous.

To obtain glossy ink-attracting layers, the particle size of the pigment should preferably be less than 500 nm. To obtain a porous glossy layer which can serve as an ink-receptive layer with rapid ink uptake, the pigment-to-binder ratio should be at least 4. Only at such high ratios is the binder no longer able to fill all the pores and voids produced by the pigments in the coating. For the porosity of the coating to be sufficient for rapid ink absorption, the pore volume of these high pigment coatings should be greater than 0.1 ml per gram of solids applied. This pore volume can by Gasad sorption (nitrogen) or mercury diffusion.

The Ink-receptive layer may be a single layer or one be composed of two or even more layers arrangement. In the latter cases is or are the polymeric binder and / or the pigment in one of the layers, in different layers or in all Layers included.

Except the The above-described main ingredients may further include a mordant acting cationic substance used in the ink-attracting layer become. Such substances enhance the ability of the layer, the dye to fix and hold the ink drop. A particularly suitable Compound is a poly (diallyldimethylammonium chloride) or abbreviated a Poly (DADMAC). These connections are through different companies available, 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 SO ₂ , 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 DADMAC 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 , m MADAME (methacrylate dimethylamine ethyl = dimethylamine ethyl methacrylate) or MADQUAT (methacryloxyethyl trimethyl ammonium chloride) modified polymers, 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 of 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, trademark 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, polyethylenimine un d Polyethyleneimine copolymers, eg, LUPASOL, trademark of BASF AG, triethanolamine tartan chelate, eg TYZOR, trademark 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 , Trademarks 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 from BAYER AG, phosphonium compounds, such as those in EP 609 930 and other cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.

The ink-attracting layer and an optional auxiliary layer, such as a backing layer serving as a roll-protective layer, can or can also commonly known conventional Ingredients, such as serving as pouring additives Surfactants, hardeners, Plasticizer, whitener and matting agents, included.

Surfactants may be used in the layers of the recording element of the invention. These surfactants can be cationic, anionic, amphoteric and nonionic surfactants, as described in US Pat JP 62-280068 (1987). Examples of surfactants are N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts and alkylnaphthalenesulfonic acid salts, sulfosuccinic acid salts, α-olefinsulfonic, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, Alkylethersulfonsäuresalze, Alkylallylethersulfonsäuresalze, Alkylamidsulfonsäuresalze, alkylphosphoric acid salts, Alkyletherphosphorsäuresalze, Alkylallyletherphosphorsäuresalze, alkyl and Alkylallylpolyoxyethylenether alkylaluminum-formaldehyde-fumed acid salts, alkylallyl ether sulfonic acid salts, alkylamide sulfonic acid salts, alkylphosphoric acid salts, alkyl ether phosphoric acid salts, alkylallyl ether phosphoric acid salts, alkyl- and alkylallyl 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, Pol Yxyethylene ethers of sorbitol esters, aliphatic acidic polyethylene glycol colester, 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, K and Na-perfluoro-C ₄ -C ₁₂ -alkylsulfonates, N-propyl-N- (2-hydroxyethyl ) perfluorooctane sulfonamide, perfluoro C ₆ -C ₁₀ alkylsulfonamidopropylsulfonylglycinate, bis (N-perfluorooctylsulfonyl-N-ethanolamine ethyl) 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 surfactants are those such as in U.S. Patent 4,781,985 described fluorocarbon surfactants of the formula F (CF ₂ ) _4-9 CH ₂ CH ₂ SCH ₂ CH ₂ N ⁺ R ₃ X ^- , in which R represents a hydrogen atom or an alkyl group, and the fluorocarbon surfactants of the formula described in US-P 5,084,340 CF ₃ (CF ₂ ) _m CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R in which 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 ink-attracting layer is generally between 0.1 and 2% by weight, preferably between 0.4 and 1.5% by weight, and most preferably 0.75% by weight on the total dry weight of the layer.

It can also be used separately in the ink-attracting a cross-linking agent Layer and / or embedded in an auxiliary layer. There is 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), oniumsubstituierte Acroleine and vinyl sulfones 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 However, the practice of the present invention is boric acid as Crosslinking agent preferred.

The ink-attracting layer and the possible auxiliary layer (s) can further comprising a plasticizer, such as ethylene glycol, diethylene glycol, Propylene glycol, polyethylene glycol, glycerol monomethyl ether, glycerol monochlorohydrin, Ethylene carbonate, propylene carbonate, urea phosphate, triphenyl phosphate, Glycerol monostearate, propylene glycol monostearate, tetramethylene sulfone, n-methyl-2-pyrrolidone and n-vinyl-2-pyrrolidone.

The different layers can after a conventional Coating technology, such as dip coating, knife coating, Extrusion coating, spin coating, cascade coating and Curtain coating, on the carrier be attached.

The The present invention will now be illustrated by the following examples. without restricting it to it.

EXAMPLES

example 1

• • Bezugsbindemittel für die vergleichende Probe: der kationische Polyvinylalkohol GOSHEFIMER K210, Warenzeichen von Nippon Gohsei, 13-1, Muroyama 2-chome, Ikaraki, Osaka 567–0052, Japan. Gohsefimer K210 weist einen Hydrolysegrad zwischen 85,5 und 88,0 mol-% auf. Eine 4%ige wässrige Lösung von Gohsefimer K210 weist eine Viskosität zwischen 18,0 und 22,0 mPa·s auf.
• • Bindemittel für die erfindungsgemäße Probe: D700, Warenzeichen von Unitika LTD, 4-1-3 Kyutara-Machi Chuo-Ku, Osaka, 541–8566 Japan, für ein modifiziertes Polyvinylalkoholcomonomer aus einem Vinylalkoholmonomer, einem Vinylacetatmonomer und einem Diacetonacrylamidmonomer. D700 hat das Aussehen cremefarbener Körnchen. Eine 4%ige wässrige Lösung weist eine mit einem Brookfield-Viskosimeter gemessene Viskosität zwischen 20 und 30 mPa·s bei 20°C auf.

The following polymeric binders are used:

• Reference binder for the comparative sample: the cationic polyvinyl alcohol GOSHEFIMER K210, trademark of Nippon Gohsei, 13-1, Muroyama 2-chome, Ikaraki, Osaka 567-0052, Japan. Gohsefimer K210 has a degree of hydrolysis between 85.5 and 88.0 mol%. A 4% aqueous solution of Gohsefimer K210 has a viscosity between 18.0 and 22.0 mPa · s.
• Binder for the sample of the present invention: D700, trademark of Unitika LTD, 4-1-3 Kyutara-Machi Chuo-Ku, Osaka, 541-8566 Japan, for a modified polyvinyl alcohol comonomer of a vinyl alcohol monomer, a vinyl acetate monomer and a diacetone acrylamide monomer. D700 has the appearance of creamy grains. A 4% aqueous solution has a viscosity measured with a Brookfield viscometer between 20 and 30 mPa · s at 20 ° C.

It become coating liquids to form ink-attracting layers, prepared by adding 30 parts by weight of solids a 40% aqueous solution of alumina (CAB-O-SPERSE PG003, available from Cabot Corp.) and 1.3 parts by weight of a 4% aqueous Boric acid solution too 7.4 parts by weight of a 10% aqueous solution of polyvinyl alcohol GOSHEFIMER K210 (available by Nippon Gohsei) for the comparative sample or to 6.3 parts by weight of a 10% aqueous solution of the modified polyvinyl alcohol D700 for the sample according to the invention are given.

The coating liquid is coated onto a subbed PET sheet (100 μm thick) by rod coating with Mayer knife and, after drying at 40 ° C, forms an ink-attracting layer with a dry coating weight of 31.5 g / m ² . The specular gloss is measured at 60 ° C and the cracking of the coating is evaluated visually.

• * TZ = Trocknungszeit

On the coalesced coating samples, primary and secondary color swatches are printed using an EPSON STYLUS Photo 870 inkjet printer (trademark of Seiko Epson Corp.). Using these color fields, the drying time and the color density can be measured. The drying time corresponds to the time after which the printed 100% cyan field can no longer be smeared with the fingers. The test results are listed in Table 1. TABLE 1 sample shine cracking TZ * (s) yellow density magenta density cyan density black density comp. 44.9 No 11 1.30 1.52 1.97 1.82 erf. 74.2 No 12 1.41 1.71 2.18 1.95

• * TZ = drying time

Out Table 1 shows that the applied and printed sample according to the invention, contains the compound D700 as a binder, with a higher gloss and higher Color densities and without sacrificing the physical properties such as drying time and tear strength.

Example 2

to Preparation of a used according to the invention polymeric binder over a semi-continuous emulsion polymerization of butyl acrylate and diacetone acrylamide is treated as follows.

10.8 g of the cationic surfactant cetyltrimethylammonium bromide are stirred at 250 revolutions / min. dissolved in a double-walled 2 liter reaction vessel with nitrogen flow in 1,412 g of water. Subsequently, the reaction vessel is heated to 85 ° C. Then, 37.8 g of butyl acrylate and 16.2 g of diacetoneacrylamide are added to the reaction vessel, and the emulsion is stirred for 5 minutes. Then, by adding a mixture of 0.54 g of a 30% aqueous H ₂ O ₂ solution and 0.81 g of ascorbic acid, a latex nucleation reaction is initiated. After completion of the latex nucleation reaction, 214.2 g of butyl acrylate and 91.8 g of diacetone acrylamide are pumped into the reaction vessel over 90 minutes. At the same time, however, an initiator solution containing a mixture of 3.06 g of a 30% aqueous solution over 110 minutes containing H ₂ O ₂ solution and 0.81 g of ascorbic acid, metered into the reaction vessel.

are All ingredients once in the reaction vessel, allowed to the reaction continues for 30 minutes, after which the residual monomer through 1-hour Distilled off vacuum distillation. The reaction vessel is opened Room temperature cooled and the latex then over coarse-grained filter paper filtered off. The emulsion polymerization gives a latex with an average particle size of 81 nm, a pH of 2.31, a viscosity of 4.3 mPa · s and a solids content of 21.0 wt .-%.

To the Making a recording medium for inkjet printing will be like proceeded in the comparative sample of Example 1, with the Difference, however, that in the preparation of the coating liquid 3.0 parts of a 21% aqueous solution instead of the polyvinyl alcohol Emulsion of the above-described polymeric binder, the butyl acrylate and diacetoneacrylamide monomers.

The application and the printing of the samples are carried out analogously to Comparative Example 1. The bleeding of colors is evaluated according to an arbitrarily chosen scale of 1 to 5, whereby 5 means the best result without bleeding colors together. The results are listed in Table 2. TABLE 2 sample shine Blossoms See Example 1 44.9 2 Example 2 56.8 3

Out Table 2 leaves It can be seen that the coated described in this Example 2 and printed inventive sample with higher Gloss and less bleeding colors than the comparative sample.

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

Claims (7)

An ink jet recording material comprising a support and at least one ink-attracting layer containing a pigment and a polymeric binder, characterized in that the polymeric binder contains a structural unit derived from a monomer of the following formula (I):

wherein R 1 is an alkyl group, R 2 is an alkyl group or aryl group, R 3 is a hydrogen atom, an alkyl group or an aryl group, L is a compound unit selected from the group consisting of CO-NH, CO-O and CO and R 4 is a hydrogen atom or an alkyl group, and Ratio of the pigment to the binder is at least 4. Ink jet recording material according to claim 1, characterized in that the polymeric binder is a copolymer of the monomer of the formula (I) and at least one other monomer selected from the group consisting of vinyl alcohol, vinylamine, allylamine, acrylates, methacrylates, acrylamides, methacrylamides, allyl ethers, Vinyl ethers, vinyl esters, styrene and styrene derivatives, vinylacetamide and vinyl formamide is. Ink jet recording material according to claim 1 or 2, characterized in that the monomer of the formula (I) Diacetone acrylamide or diacetone methacrylamide, wherein R1, R2 and R3 is a methyl group, L is CO-NH and R4 is a hydrogen atom or a methyl group. Recording material for inkjet printing after a the claims 1 to 3, characterized in that the polymeric binder a Copolymer of vinyl alcohol, vinyl acetate and diacetone acrylamide is. Recording material for inkjet printing after a the claims 1 to 3, characterized in that the polymeric binder a Copolymer of n-butyl acrylate and diacetoneacrylamide is. Recording material for inkjet printing after a the claims 1 to 5, characterized in that the pigment is an inorganic Pigment is. Ink jet recording material according to claim 6, characterized in that the inorganic pigment from the Group consisting of alumina, boehmite, pseudo-boehmite, gibbsite, Bayerite, aluminum hydroxide, silicic acid, clay, calcium carbonate, Zirconium types and mixtures of inorganic oxides and hydroxides chosen becomes.