DE60102443T2 - Multilayer ink jet recording material and its use - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to a particular type of ink jet recording material and its use in printing applications.

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, So-called stop-free printing systems have the 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, various Distracted beams at different angles and draw like that the picture on (multiple deflection system).

To a second method the ink droplets "on demand" are generated "(" 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 should be noted that the optimum composition of such an ink is the one used Ink jet printing method and depends on the type of substrate to be printed. Ink compositions can be broadly 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 Discharge 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 verlaufen 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 oder nicht-bedruckte Bereiche 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,
• – das Tintenstrahl-Aufzeichnungselement darf sowohl vor als nach dem Drucken kein Kräuseln aufweisen und nicht 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 run when 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 or non-printed areas 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,
• The ink-jet recording element must not be curled before and after printing and should not be sticky,
• - 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 absorbent 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. In U.S. Pat. No. 3,357,846 Pigments such as kaolin, talc, barite and TiO ₂ in starch and PVA are described. In 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 . U.S. Patent 4,474,850 . U.S. Pat. No. 4,547,405 . U.S. Patent 4,578,285 , WO 88 06532, U.S. Patent 4,849,286 . EP 339 604 . EP 400 681 . EP 407 881 . EP 411 638 and U.S. Pat. No. 5,045,864 (not complete list) has been described.

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.

Of further can the water resistance the applied printing ink receiving layer known by different types of film-forming polymers, an increase cause adhesion of the printing ink-receiving layer to the support, be improved.

It is known that the water resistance of the final printed image can also be improved by embedding cationic pigment-donating polymers with cationic quaternary groups such as ammonium, sulfonium and phosphonium groups. The interaction between these polymers and the majority of typical inks for ink jet printers results in better anchoring of the dye in the binder. Typical examples of such descriptions are U.S. Patent 4,371,582 . U.S. Patent 4,575,465 . U.S. Patent 4,649,064 . GB 2 210 071 and EP 423 829 ,

In EP-A 0 407 881 there is described a tack-free printing receiving member comprising (1) a color receiving layer, (2) a gelatin adhesive layer, (3) a conventional resin adhesive layer, (4) a carrier, (5) an adhesive layer, and (6) an antistatic layer contains.

In EP-A 0 469 595 there is disclosed a recording sheet comprising in sequence (1) a color-receiving layer, (2) a carrier sheet, (3) a heat-absorbing layer, and (4) a roll-protective layer.

In U.S. Pat. No. 5,888,629 An ink-jet recording medium will be described which comprises, in order, (1) a dye-receiving layer, (2) a solvent-absorbing layer, (3) an acrylic resin adhesive layer, (4) a substrate, and (5) an antistatic layer.

• – Anhaften der Vorderseite an der Rückseite des gerade hergestellten Tintenstrahlaufzeichnungselements, das als eine Bahn aufgewickelt oder nach Zuschneiden gestapelt ist,
• – Anziehung von Staub des durch Tintenstrahldruck bedruckten Materials während dessen Verwendung als Master bei der Belichtung einer Druckplatte wie einer Offsetplatte oder einer Siebdruckplatte oder eines Kontaktduplizierfilms, wobei der Anziehung triboelektrische Unterschiede zugrunde liegen,
• – unzulängliche Schärfe der gedruckten Punkte,
• – unzulängliche Beständigkeit gegen Verlaufen,
• – Transportprobleme während des Druckvorgangs,
• – unzureichende Dichte von Vollflächen des Druckbildes,
• – Wanderung von Druckfarbe von der Druckseite zur Rückseite während gelegentlichem Aufrollen des Films während des Druckvorgangs,
• – unzulängliche Maßhaltigkeit. Diese Eigenschaft ist dann von äußerster Wichtigkeit, wenn die Druckbilder auf der Basis von digital gespeicherter, mehr als einem Farbauszug entsprechender Information erzeugt und die Druckbilder als Master verwendet werden.

Many of the described commercial ink jet recording materials involve one or more of the following disadvantages

• Adhering the front side to the back side of the just-produced ink jet recording element wound as a web or stacked after cutting,
• Attraction of dust of the inkjet printed material during its use as a master in the exposure of a printing plate such as an offset plate or a screen printing plate or a contact duplicating film, wherein the attraction is based on triboelectric differences,
• - insufficient sharpness of the printed dots,
• - insufficient resistance to bleeding,
• - transport problems during the printing process,
• Insufficient density of full areas of the printed image,
• Migration of ink from the print side to the backside while occasionally rolling up the film during the printing process,
• - insufficient dimensional accuracy. This feature is of utmost importance if the print images are generated based on digitally stored information of more than one color separation and the print images are used as the master.

TASKS OF PRESENT INVENTION

task The present invention is an ink jet recording material and method for its Use, wherein the material is an improved resistance against clinging, attraction of dust and transport problems.

A Another object of the present invention is to provide an ink jet recording element and methods for its use, the printed on the material Points a good sharpness exhibit.

A Another object of the present invention is to provide an ink jet recording element and methods for To provide its use, the material has an improved dimensional stability having.

SHORT PRESENTATION THE PRESENT INVENTION

Be solved the above mentioned Tasks by two different embodiments.

To a first embodiment become the objects of the invention solved by providing an ink jet recording material containing a translucent polyester backing and on the front of the wearer one of at least two ink receptive, a polyvinyl alcohol binder containing layer layers (A), its top layer also contains a cationic mordant and a spacer, and on the back side of the carrier a double layer bandage (B), which in turn one electronically conductive Polymer-containing latex adhesive layer and a second, a crosslinked hydrophilic binder and a backing layer containing a spacer contains.

To a second embodiment become the objects of the invention solved by providing an ink jet recording material containing a translucent polyester backing and on the front of the wearer one of at least two ink receptive, a polyvinyl alcohol binder containing layer layers (A), its top layer also contains a cationic mordant and a spacer, and on the back side of the carrier a double layer dressing (B '), the in turn, a latex adhesive layer and a second, an electronic one conductive Containing polymer and a backing layer containing a spacer.

Of the The main difference between the two embodiments is therefore the choice of the element in which the electronically conductive polymer is embedded.

One Particularly suitable electronically conductive polymer is a poly (3,4-ethylenedioxythiophene) / polystyrenesulfonate complex.

Method, the use of the disclosed materials as a master for the exposure a lithographic printing plate precursor or screen printing plate describe, be explicit as "under the scope contemplated by the present invention.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The Layer arrangement and the ingredients of the ink jet recording material according to the invention will be closer in the following described.

- The ink-receptive layers

Of the consisting of color-receiving layers layer dressing is a multi-layered bandage, the at least two layers and especially preferably contains three layers. An essential ingredient of these layers is a polyvinyl alcohol binder (PVA-binder). This PVA may be a non-modified, for Part or almost completely hydrolyzed PVA. To commercially available unmodified Counting PVA binders e.g. MOWIOL, trademark of Hoechst AG, POLYVIOL WX 48/20, trademark by Wacker Co., or AIRVOL 230, trademarks of Air Products Co. The PVA may also be modified, e.g. a cationic one PVA such as GOHSEFIMER K-210, trademark of Nippon Goshei Co., or a silanol-modified PVA, such as POVAL R2105, POVAL R1130 and POVAL R3109 from Kuraray CO.

Of the PVA can be used as the sole binder or small amounts other well-known hydrophilic binders such as cellulose derivatives, Gelatin, polyvinylpyrrolidone, etc. are admixed.

At least the cover layer of the multi-layered ink-receiving layer dressing contains furthermore, a cationic mordant and a spacer.

One example for a useful cationic mordant is a cationic polyurethane, such as WITCOBOND 213, trademark of Crompton Corp.

Further suitable cationic compounds are poly (diallyldialkylammonium chloride) compounds, e.g. a poly (diallyldimethylammonium chloride) or abbreviated one Poly (DADMAC). These compounds are available through various companies such as. Aldrich, Calgon, Clariant, BASF, EKA Chemicals, Nalco Italiana and Nippon Goshei.

Other useful cationic compounds include dadmac copolymers such as copolymers with acrylamide, dimethylamine-epichlorohydrin copolymers, eg 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, cationis Cellulose derivatives such as CELQUAT L-200, H-100, SC-240C, SC-230M, trademarks of Starch & Chemical Co., and QUATRISOFT LM200, the UCARE polymers 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, trademark of BASF AG, triethanolamine tartan chelate, eg TYZOR, trademark of Du Pont Co., copolymers of vinylpyrrolidone such as VIVIPRINT 111, trademark of ISP, methacrylamidepropyldimethylamine copolymer with dimethylamine ethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trademark from ISP, 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 , and phosphonium like the ones in EP 609 930 . described Other cationic compounds include cationic alumina, cationic boehmite, and poly (aluminum hydroxychloride) such as SYLOJET A200, trademark of Grace Co. Other cationic polymers include polyvinylamines, eg PVAM-0595B from Esprit Co., cationic modified acrylic resins, eg ACRIT RKW319SX, trademark of Tasei Chemical Industries, and RD134 from Goo Chemical.

• – die in US 4 861 818 beschriebenen kugelförmigen polymeren Perlen,
• – die in US 4 906 560 und EP 589 407 beschriebenen alkalilöslichen Perlen,
• – die in EP 466 982 beschriebenen unlöslichen polymeren Perlen,
• – Polymethylmethacrylatperlen,
• – Copolymere aus Methacrylsäure und Methyl- oder Ethylmethacrylat,
• – TOSPEARL-Siloxanteilchen, Warenzeichen von Toshiba Co.,
• – SEAHOSTAR-Polysiloxan-Kieselsäure-Teilchen (z.B. Typ KE-P50), Warenzeichen von Nippon Shokubai Co.,
• – CHEMIPEARL, kugelförmige polymere Teilchen, erhältlich durch Misui Petrochemical Industries, Ltd.

The nature and ratio of the spacer contained in the overcoat of the ink receptive layer dressing should be selected to provide the best compromise between full area density and clarity of the non-printed areas. The spacers are therefore preferably transparent beads. Some classes of useful spacers are mentioned below

• - in the U.S. 4,861,818 described spherical polymeric beads,
• - in the US 4,906,560 and EP 589 407 described alkali-soluble beads,
• - in the EP 466 982 described insoluble polymeric beads,
• - polymethylmethacrylate beads,
• Copolymers of methacrylic acid and methyl or ethyl methacrylate,
• TOSPEARL siloxane particles, trademarks of Toshiba Co.,
• SEAHOSTAR polysiloxane-silica particles (eg KE-P50 type), trademark of Nippon Shokubai Co.,
• CHEMIPEARL, spherical polymeric particles, available from Misui Petrochemical Industries, Ltd.

One preferred spacer is polymethyl methacrylate or a polymethyl methacrylate derivative. One very useful derivative is a copolymer of methyl methacrylate and Stearyl methacrylate (98% / 2%), which is mixed with a polymer of styrene, maleic and sodium salt is stabilized. This compound is preferably applied as a gelatin-containing dispersion in one layer.

Except the according to the invention important Ingredients can the ink-receiving layers further other types of substances contain.

Preferably contain one or more surfactants, which are from the numerous chosen surfactant classes can be. Especially suitable are cationic surfactants, e.g. N-alkyl dimethyl ammonium chloride, Palmityltrimethylammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, an ethoxylated alkylguanidinamine complex, oleamine hydroxypropyl bistrimonium chloride, Oleylimidazoline, stearylimidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, Cocotrimonium chloride, alkyl polyglycol ether ammonium sulfate, ethoxylated Oleamine, laurylpyridine chloride, N-oleyl-1,3-diaminopropane, stearamidopropyldimethylamine lactate, coconut fatty acid amide, Oleylhydroxyethylimidazoline, isostearylethylimidethosulfate, lauramidopropyl PEG-dimonium chloride phosphate, Palmityltrimethylammonium chloride and cetyltrimethylammonium bromide.

Optional the color-receiving layers contain pigments in small amounts, which are to be dimensioned so that they are transparent throughout Inkjet recording element does not affect.

When Pigment may be an organic material such as polystyrene, polymethyl methacrylate, Silicones, urea-formaldehyde condensation polymers, polyesters and polyamides are used. However, an inorganic is preferred porous Pigment such as silica, Talc, clay, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, Aluminum hydroxide, alumina, titania, zinc oxide, barium sulfate, Calcium sulfate, zinc sulfide, satin white, boehmite and pseudo-boehmite.

The 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 carrier, the adhesive layers and the backing layers

The support of the ink jet recording material used in the present invention is a light-transmitting polyester support, for example, a polyethylene terephthalate or polyethylene naphthalate support. A support of polyethylene terephthalate (PET) is preferred. This carrier is coated on both sides with a so-called Latexhaftschicht. An essential ingredient of this latex adhesive layer is an adhesion-promoting latex. A preferred class of latex polymers suitable for this purpose relates to vinylidene chloride-containing copolymers having carboxyl functional groups. Typical examples of such polymers are (1) copolymers of vinylidene chloride and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, (2) copolymers from vinylidene chloride and a half ester of an unsaturated carboxylic acid such as the monomethyl ester of itaconic acid, (3) terpolymers of vinylidene chloride, itaconic acid and an alkyl acrylate or methacrylate such as ethyl acrylate or methyl methacrylate and (4) terpolymers of vinylidene chloride, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

In a most preferred embodiment is the latex polymer a copolymer of vinylidene chloride, methyl acrylate and itaconic acid (88% / 10% / 2%). This copolymer is prepared by emulsion polymerization using of 0.5% MERSOLAT H (trademark of Bayer AG) as emulsifying agent produced. It has the latex an additional surfactant, a so-called Nachstabilisator, be added to ensure good storage stability. Excellent storage stability let yourself with 4% ULTRAVON W, trademark of Ciba-Geigy, or DOWFAX, trademark from Dow, received.

When Another preferred ingredient of the casting solution for the latex adhesive layer can colloidal silica be added. A preferred compound is KIESELSOL 100F (Trademark of Bayer AG) with an average particle size between 25 and 30 nm. The ratio of the latex to the silica is preferably about 80/20.

The Latex adhesive layer may further contain surfactants and biocides.

One essential feature of the first embodiment of the invention it is that the latex adhesive layer on the back of the wearer of the another an electronically conductive Contains polymer. Substances with electronic conductivity instead of ionic conductivity have a non-moisture conductivity and are special suitable for use in the preparation of antistatic layers with permanent and reproducible conductivity.

Lots the known electronically conductive Polymers are strongly colored, making them less suitable for use in color separation films, however, certain of them are of the group of polyarenemethylidenes, e.g. Polythiophene and polyisothionaphthene, translucent without disturbing Coloring, at least when she's in thin Layers are embedded. Polythiophene derivatives are therefore one preferred type of conductive Compounds for use in the present invention.

The Production of conductive Polythiophenes is described in the aforementioned book "Science and Applications of Conducting Polymers ", P. 92, mentioned Production literature described.

For environmental reasons, as far as possible, the application of antistatic layers should be carried out from an aqueous solution and the amount of organic solvents should be limited as much as possible. The preparation of antistatic layers of aqueous casting compositions which are dispersions of polythiophenes in the presence of polyanions is disclosed in U.S. Pat EP-A 440 957 described. Thanks to the presence of the polyanion, the polythiophene compound is kept in dispersion.

Preferably, the polythiophene contains thiophene nuclei substituted with at least one alkoxy group or a -O (CH ₂ CH ₂ O) _n CH ₃ group, where n is a number from 1 to 4, or very particularly preferably thiophene nuclei in which a ring closure via two oxygen atoms is obtained to an optionally substituted alkylene group.

in der R¹ und R² jeweils unabhängig voneinander ein Wasserstoffatom oder eine C_1-4-Alkylgruppe oder zusammen eine gegebenenfalls substituierte C_1-4-Alkylengruppe oder eine Cycloalkylengruppe, vorzugsweise eine Ethylengruppe, eine gegebenenfalls alkylsubstituierte Methylengruppe, eine gegebenenfalls C_1-12-alkyl- oder phenylsubstituierte 1,2-Ethylengruppe, eine 1,3-Propylengruppe oder eine 1,2-Cyclohexylengruppe bedeuten.Preferred polythiophenes for use in the present invention contain structural units corresponding to the following general formula

in the R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group or together an optionally substituted C _1-4 alkylene group or a cycloalkylene group, preferably one Ethylene group, an optionally alkyl-substituted methylene group, an optionally C _1-12 alkyl or phenyl-substituted 1,2-ethylene group, a 1,3-propylene group or a 1,2-cyclohexylene group.

Very particular preference is given to poly (3,4-ethylenedioxythiophene) (PEDT) of the following formula

The preparation of the polythiophene and aqueous dispersions containing polythiophene and polymeric polyanion compounds containing the above polythiophene is mentioned in the above EP-A 0 440 957 described.

suitable polymeric polyanion compounds needed to form the polythiophenes in dispersion are acid polymers in free acidic or neutralized form. The acid polymers are preferably polymeric sulfonic acids. Examples of such polymeric acids are polymers that are acrylic acid, methacrylic acid, maleic acid, vinylsulfonic and styrenesulfonic acid or mixtures thereof.

The content of anionic groups in the anionic acidic polymers used in combination with the dispersed polythiophene polymer is preferably more than 2% by weight, based on the polymeric compounds, in order to impart sufficient stability to the dispersion. Suitable acid polymers or corresponding salts are, for example, in DE-A 2 541 230 . DE-A 2 541 274 . DE-A 2 835 856 . EP-A 14 921 . EP-A 69 671 . EP-A 130 115 . U.S. Patent 4,147,550 . U.S. Patent 4,388,403 and U.S. Pat. No. 5,006,451 described.

The weight ratio of the polythiophene polymer to the polymeric polyanion compound (s) vary within wide limits, but preferably lies between about 50/50 and 15/85.

One most preferred polymeric polyanion for use in Combination with the polythiophene derivative, e.g. PEDT, is polystyrene sulfonate (PSS).

Though becomes a polythiophene-polyanion complex as an electronically conductive substance preferably, but other substances are suitable, e.g. polypyroles, Polyanilines, sulfonated poly-p-phenylenes, sulfonated polyfluorenes, optionally carboxylated or sulfonated polyphenylenevinylenes and optionally carboxylated or sulfonated polythienylenevinylenes. Optionally, you can these polymers also as a complex with a polymeric polyanion, e.g. Polystyrenesulfonate be used.

In the first embodiment of the invention contains the layering (B) on the back except the Latex adhesive layer with the conductive Compound a second backing layer, the a crosslinked hydrophilic binder and a spacer contains.

In a preferred embodiment, the hydrophilic binder of the second backing layer is gelatin. Suitable crosslinking agents (or hardeners) include those of the epoxide type, the ethyleneimine type, the vinylsulfone type such as 1,3-vinylsulfonyl-2-propanol, chromium salts, eg, chromium acetate and chromium alum, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin, dioxane derivatives such as 2,3-dihydroxydioxane, active vinyl compounds, eg 1,3,5-triacryloylhexahydro-s-triazine, active halogen compounds such as 2,4-dichloro 6-hydroxy-s-triazine, and mucohalogenic acids such as mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. The gelatin can also be treated with fast curing agents such as carbamoylpyridinium salts of the in US Pat. No. 4,063,952 hardened type described. In a preferred embodiment, the curing agent is a vinylsulfone.

The second backing layer contains further a spacer. This spacer can be made from the same types as for the topcoat of the ink-receptive layers are described. A a particularly suitable compound is also a copolymer here from methyl methacrylate and stearyl methacrylate (98% / 2%), which with a Polymer of styrene, maleic acid and sodium salt is stabilized. This compound is preferably embedded as a gelatin-containing dispersion in the second backing layer.

In a second embodiment of the invention contains the layer structure (B ') on the back side of the polyester carrier one to the wearer next lying latex adhesive layer and an electronically conductive layer as a second backing layer. In this embodiment contains the latex adhesive layer preferably no or substantially no electronic conductive Connection. Furthermore, the composition is that for the latex adhesive layer the first embodiment similar composition described. In the second embodiment is the electronically conductive Compound in the second backing layer contain. This electronically conductive connection is preferred from the same compounds as above for the first embodiment described selected. Again, a particularly suitable compound is the poly (3,4-ethylenedioxythiophene) / polystyrenesulfonate complex. The layer contains furthermore a spacer, preferably made of the above Classes elected becomes. A very suitable connection is also here Copolymer of methyl methacrylate and stearyl methacrylate (98% / 2%), stabilized with a polymer of styrene, maleic acid and sodium salt is. The binder of this backing layer may be hydrophilic or hydrophobic. A preferred binder is a film-forming polymethyl methacrylate. Furthermore, this can Layer other ingredients such as biocides and surfactants included.

The Latex adhesive layer on the front of the polyester carrier has preferably substantially the same composition as the Latex adhesive layer on the back, but preferably contains they are not electronically conductive Polymer.

Furthermore, a so-called gelatin adhesive layer is also embedded on the front side between the latex adhesion layer and the ink-receiving layers. In a preferred embodiment, this gelatin adhesive layer contains a mixture of gelatin and colloidal silica. A preferred compound is also KIESELSOL 300F (trademark of Bayer AG). A softening compound may be used to prevent hairline cracking in the dried layer due to excessive shrinkage of the layer during drying. Plasticizers are well known to those skilled in the art. For this purpose, both low molecular weight compounds (eg acetamide, glycerol) are suitable as polymeric latexes (eg, polyethyl acrylate, poly-n.-butyl acrylate). Furthermore, the gelatin adhesive layer may contain one or more surfactants. Usable surfactants include ULTRAVON ^™ W, an arylsulfonate from CIBA-GEIGY, DOWFAX from Dow CO., And ARKOPAL ^™ N060 (formerly HOSTAPAL ^™ W), a nonylphenylpolyethylene glycol from HOECHST. The thickness of the gelatin adhesive layer is preferably between 0.1 and 1 μm.

- Coating technology

In a particularly preferred embodiment The order is made of the two latex adhesive layers, the gelatin adhesive layer and the second backing layer "on line" in a continuous process in the manufacturing area of the polyester itself. Molten polyester is extruded and longitudinally stretched. Subsequently the first latex adhesive layer is placed on top and the second, optionally conductive Latex adhesive layer attached to the back. Thereafter, the subbed polyester is cross-stretched. The gelatin adhesive layer is placed on top and finally becomes the second backing layer on the backsheet applied.

Of the The ink-receiving layers are applied "off line". There is also any coating technology in question, such as dip coating, air brush coating, cascade coating and curtain coating.

- Using an inkjet image as a printmaster.

• (1) die wie oben beschriebene Herstellung eines erfindungsgemäßen Tintenstrahlaufzeichnungsmaterials,
• (2) den informationsmäßigen Auftrag von Tropfen einer UV-absorbierenden Tinte auf die Stirnfläche des Tintenstrahlaufzeichnungsmaterials mittels eines Tintenstrahldruckers, wodurch ein Druckbild erzeugt wird,
• (3) Gesamtbelichtung mit aktinischem Licht einer lithografischen Druckplattenvorstufe durch eine aus dem in den Schritten (1) und (2) erzeugten Druckbild bestehende Maske,
• (4) Entwicklung der belichteten lithografischen Druckplattenvorstufe zu einer lithografischen Druckplatte.

An inkjet image formed imagewise from digitally stored information may be used as a master for the lithographic printing plate exposure. This method comprises the following steps in sequence

• (1) the production of an ink jet recording material of the present invention as described above,
• (2) the informational deposition of drops of a UV absorbing ink on the end face of the ink jet recording material by means of an ink jet printer, thereby producing a printed image,
• (3) total exposure to actinic light of a lithographic printing plate precursor through a mask consisting of the print image formed in steps (1) and (2),
• (4) Development of the exposed lithographic printing plate precursor into a lithographic printing plate.

When The ink used for image formation may be any type of ink be used. But preferred are water-based inks. Although the UV absorbing colorant of the ink is preferable Gastruss, but in principle can also be a mixture of dyes, The black results are to be used, provided that the UV density sufficient.

at Multi-color printing can different printing plates through different inkjet masks, the from digital, different color separations corresponding information are obtained, be exposed. This application explains the Importance of dimensional stability of the ink-jet material according to the invention.

• (1) die wie oben beschriebene Herstellung eines erfindungsgemäßen Tintenstrahlaufzeichnungsmaterials,
• (2) den informationsmäßigen Auftrag von Tropfen einer UV-absorbierenden Tinte auf die Stirnfläche des Tintenstrahlaufzeichnungsmaterials mittels eines Tintenstrahldruckers, wodurch ein Druckbild erzeugt wird,
• (3) Gesamtbelichtung mit aktinischem Licht einer Siebdruckplatte durch eine aus dem in den Schritten (1) und (2) erzeugten Druckbild bestehende Maske,
• (4) Entwicklung der belichteten Siebdruckplatte zu einem Siebdruckelement.

Also, the ink jet image can be used as a mask for exposure of a screen printing plate. This method comprises the following steps in sequence

• (1) the production of an ink jet recording material of the present invention as described above,
• (2) the informational deposition of drops of a UV absorbing ink on the end face of the ink jet recording material by means of an ink jet printer, thereby producing a printed image,
• (3) total exposure to actinic light of a screen printing plate by a mask composed of the print image formed in steps (1) and (2),
• (4) Development of the exposed screen printing plate into a screen printing element.

Similarly, are also multi-color printing and printing with different spot colors, e.g. on fabric, possible.

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

EXAMPLES

EXAMPLE 1

1.1 Composition of according to the invention and comparative materials

- Composition of material according to the invention 1 according to the first embodiment

On the front of a PET carrier become three color-absorbing layers, the polyvinyl alcohol (MOWIOL) as a binder, applied. The cover layer further contains a polyurethane with cationic groups (WITCOBOND) and as a spacer a copolymer of methyl methacrylate and stearyl methacrylate (98% / 2%), stabilized with a polymer of styrene, maleic acid and sodium salt is. Between the ink-receiving layer dressing and the PET carrier "on line" a latex adhesive layer, the as essential constituents a from a copolymer of vinylidene chloride, Methyl acrylate and itaconic acid (88% / 10% / 2%) existing latex adhesive, colloidal silica and Contains surfactants, and a gelatin adhesive layer containing gelatin as essential ingredients and colloidal silica contains inserted.

The first backing layer is an electronically conductive Latex adhesive layer, which consists of a copolymer of vinylidene chloride, Methyl acrylate and itaconic acid Latex adhesive (88% / 10% / 2%) and a poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate complex as the conductive polymer contains. Furthermore contains they colloidal silica (KIESELSOL 100F), a surfactant and a biocide. The second backing layer contains with a divinylsulfone hardener crosslinked gelatin and as matting a gelatin-containing dispersion a copolymer of methyl methacrylate and stearyl methacrylate (98% / 2%), which with a polymer of styrene, maleic acid and Sodium salt is stabilized.

- Composition of material according to the invention 2 according to the second embodiment

The Composition of the front side is the same as in the material according to the invention 1. The first backing layer is a latex adhesive layer, that of the latex adhesive layer of example 1.1 is the same, but without electronically conductive connection. The second backing contains a poly (3,4-ethylenedioxythiophene) / polystyrenesulfonate complex as a conductive Polymer, as a spacer, a copolymer of methyl methacrylate and Stearyl methacrylate (98% / 2%), which is mixed with a polymer of styrene, maleic and sodium salt stabilized, colloidal silica, a Polyethylene emulsion and film-forming polymethylmethacrylate as Binder.

- comparative materials

Comparative Material 1: AJM CLEAR FILM, a commercial material sold by Agfa-Gevaert on the base of one attached to both sides of the material Binder mixture of gelatin and polyvinylpyrrolidone.

Comparative Material 2: Epson Transparant (5041063), a commercial grade translucent microporous Boehmite-based material.

1.2 Evaluation of physical properties

1.2.1 mean particle size on one Epson 3000 printer

• Inventive material 1: 62 μm,
• Comparative material 2: 74.5 μm.

1.2.1 Examination of the adhesivity

The printed front sides of the inventive and comparative materials become after 10minütiger Drying pressed against different backing layers and Kept for 24 hours.

The tested Backing bandages are the back layer bandages of the material according to the invention 1, of the material according to the invention 2 and the comparative material 1.

The printed front side of the comparative material 1 sticks to all tested backs and prevents transmission from ink from the front to the back. The printed front the material according to the invention 1 sticks only to the back of the comparative material 1 and not on the back the materials of the invention 1 and 2 and there is no transmission of printing ink.

1.2.3 Printed full-surface density

• Erfindungsgemäßes Material 1: optische Dichte 3,44, UV-Dichte 2,81
• Vergleichendes Material 1: optische Dichte 2,54, UV-Dichte 2,18

On an Epson 9000 printer (medium quality, normal dot quality):

• Inventive material 1: optical density 3.44, UV density 2.81
• Comparative material 1: optical density 2.54, UV density 2.18

1.2.4 Wipe checks

Fresh printed solid surfaces are wiped as a function of time with a small pen with cotton tip. Inventive material 1 is smudge resistant after 1 to 2 minutes while this is the case with comparative material 1 after 5 minutes.

1.2.5 Dimensional accuracy tests

In Table 1 below shows the dimensional stability values in μm / m (reversible RV coefficients). The measurements take place both in the long and in the width sliced patterns.

TABLE 1

EXAMPLE 2

Comparison of different cationic mordant

template be with the same composition as in the inventive pattern 1 coated from the previous example, but with the difference that a different cationic mordant is used in each case.

• – kationische Polyurethandispersionen: WITCOBOND 213 (siehe voriges Beispiel), ENOREX PU750, ENOREX PU950 (Warenzeichen von Collano Co.), CHROMOELASTIC C-4480 (Warenzeichen von Chromogenia-Units SA, Italien),
• – Poly(dadmac)-Varianten: CAT FLOC 71259, CAT FLOC CFL, CATFLOC CL (Warenzeichen von Nalco Italiana S.r.1., Italien),
• – Copolymere aus Dimethylamin und Epichlorhydrin : REDIFLOC 4150 (Warenzeichen von EKA Chemicals) und POLYFIX 601 (Warenzeichen von Showa High Polymer Co.).

The following connections are checked:

• Cationic polyurethane dispersions: WITCOBOND 213 (see previous example), ENOREX PU750, ENOREX PU950 (trademark of Collano Co.), CHROMOELASTIC C-4480 (trademark of Chromogenia-Units SA, Italy),
• Poly (dadmac) variants: CAT FLOC 71259, CAT FLOC CFL, CATFLOC CL (trademark of Nalco Italiana Srl., Italy),
• Copolymers of dimethylamine and epichlorohydrin: REDIFLOC 4150 (trademark of EKA Chemicals) and POLYFIX 601 (trademark of Showa High Polymer Co.).

• – alle Muster zeigen eine vergleichbare gute Dichte und Punktgröße,
• – die Polyurethane weisen bessere Trocknungseigenschaften auf,
• – die Bildqualität ist auch die beste bei den Polyurethanen.

General test results:

• All samples show a comparable good density and dot size,
• The polyurethanes have better drying properties,
• - The image quality is also the best in the case of polyurethanes.

Claims (24)

An ink jet recording material containing a translucent polyester backing and on the front of the wearer a layer dressing (A) comprising a latex adhesive layer, a gelatin adhesive layer and at least two color-receiving, a polyvinyl alcohol binder contains containing layers, wherein the cover layer of the ink-receiving layers is also a cationic mordant and a spacer, and on the back side of the carrier a double layer bandage (B), which in turn one electronically conductive Polymer-containing latex adhesive layer and a second, a crosslinked hydrophilic binder and a backing layer containing a spacer contains. An ink jet recording material according to claim 1, characterized in that the cationic mordant is cationic Polyurethane latex is. An ink jet recording material according to claim 1, characterized in that the cationic mordant is a poly (diallyldimethylammonium chloride) is. An ink jet recording material according to any one of claims 1 to 3, characterized in that the spacer in the ink receptive topcoat at the front and / or in the second backing layer a stabilized with a polymer of styrene, maleic acid and sodium salt Copolymer of methyl methacrylate and stearyl methacrylate (98% / 2%) is. An ink jet recording material according to any one of claims 1 to 4, characterized in that the layer structure (A) at the front contains three ink-receptive layers. An ink jet recording material according to any one of claims 1 to 5, characterized in that the electronically conductive polymer in the latex adhesive layer on the back a polythiophene polyanion complex is. An ink jet recording material according to claim 6, characterized in that the polythiophene is poly (3,4-ethylenedioxythiophene) is. An ink jet recording material according to claim 6, characterized in that the polyanion is polystyrene sulfonate. An ink jet recording material according to any one of claims 1 to 8, characterized in that the hydrophilic binder the second backing layer Gelatin is. Ink jet recording material according to claim 9, characterized in that the gelatin with a vinyl sulfone hardener is crosslinked. An ink jet recording material containing a translucent polyester backing and on the front of the wearer a layer dressing (A) comprising a latex adhesive layer, a gelatin adhesive layer and at least two color-receiving, a polyvinyl alcohol binder contains containing layers, wherein the cover layer of the ink-receiving layers is also a cationic mordant and a spacer, and on the back side of the carrier a double layer dressing (B '), in turn, a latex adhesive layer and a second, electronically conductive Containing polymer and a backing layer containing a spacer. An ink jet recording material according to claim 11, characterized in that the cationic mordant a cationic polyurethane latex. An ink jet recording material according to claim 11, characterized in that the cationic mordant a Poly (diallyldimethylammonium chloride). An ink jet recording material according to any one of claims 11 to 13, characterized in that the spacer in the ink receptive topcoat at the front and / or in the second backsheet a stabilized with a polymer of styrene, maleic acid and sodium salt Copolymer of methyl methacrylate and stearyl methacrylate (98% / 2%) is. An ink jet recording material according to any one of claims 11 to 14, characterized in that the layer structure (A) to the front contains three ink-receptive layers. An ink jet recording material according to any one of claims 11 to 15, characterized in that the electronically conductive polymer in the second backing layer a polythiophene-polyanion complex is. An ink jet recording material according to claim 16, characterized in that the polythiophene poly (3,4-ethylenedioxythiophene) is. An ink jet recording material according to claim 16, characterized in that the polyanion polystyrene sulfonate is. Process for the preparation of a lithographic Pressure plate, which in turn comprises following steps (1) Preparation of an ink jet recording material as defined in any of claims 1 to 18, (2) the informational order from drops of a UV absorbing Ink on the face the ink jet recording material by means of an ink jet printer, whereby a printed image is generated, (3) overall exposure with actinic light of a lithographic printing plate precursor one composed of the print image produced in steps (1) and (2) Mask, (4) Development of the exposed lithographic printing plate precursor to a lithographic printing plate. Method according to claim 19, characterized that the ink contains a gas black Water-based ink. Method according to claim 14, characterized in that that the ink is a water-based ink that is a mixture of Contains dyes that gives black. Method for producing a screen printing element, which in turn comprises the following steps (1) Production one according to one of the claims 1 to 18 defined ink jet recording material, (2) the informational order from drops of a UV absorbing Ink on the face the ink jet recording material by means of an ink jet printer, whereby a printed image is generated, (3) overall exposure with Actinic light of a screen printing plate by a from the in the Steps (1) and (2) generated print image existing mask, (4) Development of the exposed screen printing plate to a screen printing element. Method according to claim 22, characterized in that the ink is a water-based ink containing gas black. A method according to claim 22, characterized in that the ink is a water-based ink, which contains a mixture of dyes giving black.