DE10257131B4 - Coated inkjet printing material, process for its preparation - Google Patents

Abstract

wobei R¹ Wasserstoff oder Methyl bedeutet,
b.) 0 bis 99,0 Gew.-% Struktureinheiten der Formel (2)

wobei R² Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen darstellt,
c.) 0,01 bis 70,0 Gew.-% Struktureinheiten der Formel (3)

wobei R³, R⁴, R⁵ und R⁶, jeweils unabhängig voneinander Reste mit einem Molekulargewicht im Bereich von 1 bis 500 g/mol sind,
jeweils bezogen auf das Gesamtgewicht des Polymers (A) enthält,
und
B.) 0,01 bis 50,0 Gewichtsteilen mindestens einer Hydroxyverbindung (B) der Formel (4)

wobei R⁷ jeweils unabhängig voneinander Wasserstoff oder einen Alkylrest mit 1...Coated inkjet printing material, characterized in that the coating contains more than 0.1% by weight, based on its total weight, of at least one polyvinyl acetal (I) which is obtainable by a process in which a mixture of
A.) 50.0 to 99.99 parts by weight of at least one polymer (A), which
a.) 1.0 to 99.9% by weight of structural units of the formula (1)

where R ^{1 is} hydrogen or methyl,
b.) 0 to 99.0% by weight of structural units of the formula (2)

where R ^{2 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms,
c.) 0.01 to 70.0% by weight of structural units of the formula (3)

wherein R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently of one another radicals having a molecular weight in the range from 1 to 500 g / mol,
each based on the total weight of the polymer (A),
and
B.) 0.01 to 50.0 parts by weight of at least one hydroxy compound (B) of the formula (4)

where R ⁷ is, independently of one another, hydrogen or an alkyl radical having 1 ...

Description

The This invention relates to coated materials for ink jet printing, in particular those materials which lead to a more rapid printing ink drying to lead.

Of the Inkjet printing has been known for a long time and becomes, for example in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-Rom, Wiley-VCH, 1997 - Keywords: Imaging Technology 2.1.3 Ink-Jet Printing described in detail. When inkjet or ink-jet printing process by means of different processing techniques finest ink droplets thrown on the material to be printed, without it from the Pressing machine touched becomes ("non-impact printing ") Way of the droplets To print template is by computer-controlled printhead movements the inkjet printer or controlled by electrostatic deflection. The ink droplets of a few picoliters each content, the overall desired Print in the form of writing and picture.

The Base material carrying the coating to be printed is usually flat and may be absorbent in nature, such as fiber composites (e.g., paper, cardboard) and textile, or nonabsorbent, such as films (e.g., plastic, metal). The base material can already with a pigmented (bar) or pigmentless coating Equipped (primer) have been before the coating compositions described below on their surfaces be applied. The surfaces the artwork must, whether painted, primer-pretreated or untreated, wettable be equipped, which is especially important for film materials. exemplary Here are the chemical pretreatment and the corona discharge as wetting cited.

• – Druckschärfe, hohe Auflösung
• – Brillanz, hohe Farbdichte, Druckglanz
• – Farbstand, sauber abgegrenztes Druckbild
• – Homogenität des Druckes, insbesondere in den vollen Flächen
• – Trocknungsgeschwindigkeit
• – Abriebfestigkeit
• – Wasserfestigkeit

Today's generation of inkjet printers allow high-resolution images to be reproduced by means of printing in a relatively short time, placing high demands on the image-receiving materials. The following summarizes the properties which are of particular importance in the context of the present invention:

• - Print sharpness, high resolution
• - Brilliance, high color density, print gloss
• - Color level, clean demarcated print image
• - Homogeneity of pressure, especially in the full areas
• - Drying speed
• - abrasion resistance
• - water resistance

• – Das Tintentröpfchen trifft auf die Druckvorlage, auf welcher es sich idealerweise rasch auf ca. das Doppelte seines ursprünglichen Durchmessers lateral ausbreitet, seine kreisrunde Form beibehält und möglichst wenig in das Druckmedium eindringt. Durch die begrenzte Ausdehnung des Tröpfchens auf der Oberfläche bis zur leichten Überlappung mit anderen Tröpfchen wird eine gute Abdeckung der Druckvorlage erreicht.
• – Während die feste Phase der Ink-Jet-Druckfarbe, insbesondere die Farbstoffe, möglichst an der Oberfläche verbleiben sollen, ist es erwünscht, dass die fluide Phase der Ink-Jet-Druckfarbe so rasch wie möglich in die Bildempfangsschicht, gegebenenfalls auch in Schichten darunter, wegschlägt. Hierdurch wird eine schnelle Trocknung ermöglicht.
• – Beide vorgenannten Vorgänge müssen absolut gleichmäßig ablaufen, damit bei makroskopischer Betrachtung jede Farbe für sich zu einem homogenen Druckbild von einheitlicher Densität beisteuert.
• – Druckfarben von aneinandergrenzenden Druckbereichen dürfen nicht ineinander laufen (bleeding), was in der Regel nicht stattfindet, wenn die Druckfarben rasch trocknen.
• – Wie bereits vorstehend beschrieben, ist die Oberfläche der Druckvorlage durch Behandlung, Ausrüstung oder Beschichtung so beschaffen, dass sich die Farbstoffkörper der applizierten Druckfarben gut adsorbieren bzw. fixieren lassen. Damit ist gewährleistet, dass der Ink-Jet-Druck nicht abgewischt oder abgerieben werden kann.
• – Bei wasserfesten Ausrüstungen der Papieroberfläche wird die Ink-Jet-Druckfarbe oberflächennah auf eine solche Weise eingebettet und fixiert, dass die Farbkörper weitgehend vor Wasser geschützt sind. Die Zusammensetzung der Beschichtung ist auf diese Forderung besonders abgestellt.

The process of the printing process until the completed text or image representation is generally as follows:

• The droplet of ink strikes the original on which it ideally spreads out laterally to approximately twice its original diameter, retains its circular shape and penetrates as little as possible into the print medium. Due to the limited expansion of the droplet on the surface to the slight overlap with other droplets, a good coverage of the artwork is achieved.
• While the solid phase of the ink-jet printing ink, in particular the dyes, should as far as possible remain on the surface, it is desirable for the fluid phase of the ink-jet printing ink to enter the image-receiving layer as quickly as possible, and optionally also layers underneath , strikes away. As a result, a quick drying is possible.
• Both of the aforementioned processes must proceed absolutely uniformly, so that on macroscopic consideration each color contributes to a homogeneous printed image of uniform density.
• - Printing inks from adjacent printing areas must not bleed, which usually does not occur when the inks dry quickly.
• - As already described above, the surface of the master by treatment, equipment or coating is such that the dye body of the applied printing inks can be well adsorbed or fixed. This ensures that the inkjet printing can not be wiped off or rubbed off.
• - For waterproof paper surface equipment, the inkjet ink is embedded and fixed near the surface in such a way that the color bodies are largely protected from water. The composition of the coating is particularly adapted to this requirement.

The use of polyvinyl alcohols and polyvinyl acetals as binders in ink jet printing is already known from the literature. For example, the publications describe DE 41 16 595 A1 . EP 0 379 964 A1 and EP 0 423 829 A1 Receiving layers for ink jet printing containing silica, a cationic polymer and polyvinyl alcohol. The pamphlets JP11240246A1 and JP2038088 A1 disclose inkjet printing receiving layers comprising polyvinyl acetals. Furthermore, the publications DE 195 34 327 A1 and JP3197511 Inkjet printing inks which contain polyvinyl alcohol or polyvinyl acetals as a binder.

The Use of such materials in inkjet printing provides in usually satisfactory results. However, the disadvantage is the long drying times of the ink as well as the particular in Comparison with other printing techniques, such as laser printing, low quality of the printed image.

DE 199 33 139 A1 relates to pigment dispersions for recording media containing polyvinyl acetals, which may additionally comprise polyvinyl alcohol etherified with oligo- or polyethylene glycol or oligo- or polypropylene glycol etherified.

DE 694 03 396 T2 describes an ink jet recording process using conventional polyvinyl alcohol.

DE 694 03 566 T2 discloses recording means for ink jet printing comprising an ink receiving layer of polyvinyl alcohol, polyalkylene oxide and a hydrophilic acrylic resin.

DE 100 11 096 A1 relates to the use of carboxyl-containing acetal polymers in photosensitive compositions and lithographic printing plates.

US 5,332,774 describes plasticized polyvinyl acetal resins comprising a polyvinyl acetal and a plasticizer, such as a glycol ether.

US 5,989,650 discloses an ink jet printing medium comprising an ink-receiving layer made from a partially acetalized polyvinyl alcohol.

DE 101 20 492 A1 relates to the use of etherified vinyl alcohol polymers as thickeners.

The post-published DE 102 29 213 A1 discloses the polyvinyl acetals used in the invention and their preparation, but not their use as a receiving layer for ink jet printing.

DE 40 33 775 A1 describes Pfropfpolyvinylacetale acetal groups with etherified w-hydroxy (poly) alkoxyalkanalen.

• – die Adhäsion der Druckfarbe auf der bedruckten Beschichtung;
• – der Folienglanz bzw. der Papierglanz;
• – die Intensität der Farben;
• – die Homogenität der Farben;
• – die Druckschärfe;
• – der Druckglanz;
• – die Trocknungsgeschwindigkeit der Druckfarbe und
• – die Wasserfestigkeit Druckfarbe

nach Möglichkeit verbessert werden. Gleichzeitig sollte ein Ineinanderlaufen der Druckfarben, das sogenannte "bleeding", nach Möglichkeit vermieden werden.In view of this prior art, it was therefore an object of the present invention to provide coated materials which allow ink jet printing faster drying of the ink while providing an improved print image. In particular, should

• The adhesion of the ink to the printed coating;
• - the film gloss or paper gloss;
• - the intensity of the colors;
• - the homogeneity of the colors;
• - the print sharpness;
• - the printing gloss;
• The drying speed of the ink and
• - the water resistance printing ink

to be improved if possible. At the same time, bleeding of the printing inks, if possible, should be avoided.

A The object of the present invention was also to be seen therein Process for the preparation of the coated materials according to the invention specify in a simple manner, on an industrial scale and economical feasible are.

Be solved these as well as other not explicitly mentioned tasks, however from the contexts discussed hereinbefore readily derivable or accessible are, by a coated material with all features of the claim 1. Appropriate modifications Coated according to the invention Materials are disclosed in the subclaims referring back to claim 1 Protection provided. The requirements The process category describes preferred approaches to Preparation of the coated invention Material.

• A.) 50,0 bis 99,99 Gewichtsteilen mindestens eines Polymers (A), welches a.) 1,0 bis 99,9 Gew.-% Struktureinheiten der Formel (1)
  
  wobei R¹ Wasserstoff oder Methyl bedeutet, b.) 0 bis 99,0 Gew.-% Struktureinheiten der Formel (2)
  
  wobei R² Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen darstellt, c.) 0,01 bis 70,0 Gew.-% Struktureinheiten der Formel (3)
  
  wobei R³, R⁴, R⁵ und R⁶, jeweils unabhängig voneinander Reste mit einem Molekulargewicht im Bereich von 1 bis 500 g/mol sind, jeweils bezogen auf das Gesamtgewicht des Polymers (A) enthält, und
• B.) 0,01 bis 50,0 Gewichtsteilen mindestens einer Hydroxyverbindung (B) der Formel (4)
  
  wobei R⁷ jeweils unabhängig voneinander Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen bedeutet, R⁸ Wasserstoff oder einen Alkylrest mit 1 bis 10 Kohlenstoffatomen darstellt und n eine Zahl größer gleich 2 ist, mit
• C.) mindestens einer Verbindung (C) der Formel (5) umsetzt,
  
  wobei R⁹ und R¹⁰ jeweils unabhängig voneinander Wasserstoff, COOH, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine gegebenenfalls substituierte Arylgruppe mit 6 bis 12 Kohlenstoffatomen sind,

wobei man pro mol Hydroxylgruppen, die das Polymer (A) und die Hydroxyverbindung (B) in Summe enthalten, 0,0005 bis 0,5 mol der Verbindung (C) einsetzt,
gelingt es auf nicht ohne weiteres vorhersehbare Weise, ein beschichtetes Material für die Tintenstrahlbedruckung zugänglich zu machen, welches im Vergleich mit herkömmlichen beschichteten Materialien eine schnellere Trocknung der Druckfarbe erlaubt.By providing a coated material characterized in that the coating contains, based on its total weight, more than 0.1% by weight of at least one polyvinyl acetal (I) which is obtainable by a process in which a mixture of

• A.) 50.0 to 99.99 parts by weight of at least one polymer (A) which contains a) 1.0 to 99.9% by weight of structural units of the formula (1)
  
  where R ^{1 is} hydrogen or methyl, b.) 0 to 99.0% by weight of structural units of the formula (2)
  
  where R ^{2 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, c.) 0.01 to 70.0% by weight of structural units of the formula (3)
  
  wherein R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently radicals having a molecular weight in the range of 1 to 500 g / mol, based in each case on the total weight of the polymer (A), and
• B.) 0.01 to 50.0 parts by weight of at least one hydroxy compound (B) of the formula (4)
  
  wherein R ⁷ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, R ^{8 is} hydrogen or an alkyl group having 1 to 10 carbon atoms and n is a number greater than or equal to 2, with
• C.) reacting at least one compound (C) of the formula (5),
  
  wherein R ⁹ and R ^{10 are} each independently of one another hydrogen, COOH, an alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms,

wherein 0.0005 to 0.5 mol of the compound (C) is used per mole of hydroxyl groups containing the polymer (A) and the hydroxy compound (B) in total,
In a way that is not readily predictable, it is possible to provide a coated ink jet printing material which, in comparison with conventional coated materials, permits faster drying of the ink.

• – Durch das erfindungsgemäße beschichtete Material wird die Adhäsion der Druckfarbe auf der bedruckten Beschichtung sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird der Folienglanz bzw. der Papierglanz sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird die Intensität der Farben sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird die Homogenität der Farben sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird die Druckschärfe sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird der Druckglanz sowohl im Schwarz- als auch im Farbdruck in der Regel verbessert.
• – Durch das erfindungsgemäße beschichtete Material wird die Trocknungsgeschwindigkeit der Druckfarbe sowohl im Schwarz- als auch im Farbdruck in der Regel deutlich erhöht.
• – Durch das erfindungsgemäße beschichtete Material wird die Wasserfestigkeit der Druckfarbe sowohl im Schwarz- als auch im Farbdruck deutlich verbessert.
• – Das erfindungsgemäße beschichtete Material ist auf einfache Art und Weise großtechnisch und kostengünstig herstellbar.

At the same time, the coated material of the invention has a number of other important advantages. These include:

• The coated material according to the invention generally improves the adhesion of the printing ink to the printed coating in both black and color printing.
• - Due to the coated material according to the invention the film gloss or paper gloss is improved in both black and color printing in the rule.
• - The coated material according to the invention, the intensity of the colors is improved in both black and color printing in the rule.
• The coated material according to the invention generally improves the homogeneity of the colors in both black and color printing.
• - By the coated material of the invention, the print sharpness is improved in both black and color printing in the rule.
• - By coated material according to the invention the printing gloss is improved in both black and color printing in the rule.
• - Due to the coated material according to the invention, the drying speed of the ink is generally significantly increased both in black and in color.
• - The coated material according to the invention, the water resistance of the ink is significantly improved both in black and in color.
• - The coated material according to the invention can be produced in a simple manner on a large scale and inexpensively.

• – Papier und Karton,
• – Textilien aller Art,
• – Folien, insbesondere aus Kunststoff, welche, bezogen auf ihr Gesamtgewicht, vorzugsweise mehr als 50 Gew.-%, zweckmäßigerweise zu mehr als 75 Gew.-%, insbesondere zu mehr als 85 Gew.-%, aus Polyethylen, Polypropylen, Polyester, insbesondere Polyethylenterephthalat, Polyvinylchlorid, Polyacrylat, Polymethacrylat und/oder Polycarbonat enthält;
• – Aluminium sowie
• – kaschierte Laminate oder Extrudate dieser Materialien.

The present invention relates to a coated material for ink jet printing. It preferably comprises a base material which is provided on at least one side, preferably on its entire surface, with the coating according to the invention. Particularly suitable base materials in the context of the present invention include:

• - paper and cardboard,
• - textiles of all kinds,
• - Films, in particular of plastic, which, based on their total weight, preferably more than 50 wt .-%, advantageously more than 75 wt .-%, in particular more than 85 wt .-%, of polyethylene, polypropylene, polyester, in particular polyethylene terephthalate, polyvinyl chloride, polyacrylate, polymethacrylate and / or polycarbonate;
• - Aluminum as well
• Laminated laminates or extrudates of these materials.

In this context, paper in the context of the present invention refers to a flat material consisting essentially of fibers of predominantly vegetable origin, which is formed by dewatering a pulp slurry on a sieve (compare DIN 6730: 1996-05). This results in a fiber felt, which is then compressed and dried. The basis weight is generally up to 225 g / m ² . At Flächengew. > 225 g / m ² is called cardboard. For further details, reference is made to the usual specialist literature, in particular to Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999 - keyword "paper" and the sources cited at this point.

In the context of the present invention, paperboard is a flat material consisting of paper stock whose properties lie between paper and paperboard and, with regard to the basis weight of 150 to 600 g / m ^2, extends both into the field of papers and into the paperboard. He is stiffer than paper and is generally made of higher quality materials than cardboard. The designation of the different types of cardboard depends on the purpose and properties (see DIN 6730 (05/1996)).

In the context of the present invention, films designate thin, flat, flexible, windable webs of metals (very thin sheets, eg gold leaf, aluminum, tin foil = stanniol) or plastics (eg cellulose acetate, PVC, polyethylene). Particularly thin films are also called films. Metal foils are obtained by rolling or beating, plastic foils by casting, calendering or extruding, which is carried out as blow molding, whereby tube or blown films are produced, which are cut open. For further details please refer to the usual technical literature, in particular to Römpp Lexikon Chemie - Version 2.0, Stutt gart / New York: Georg Thieme Verlag 1999 - keyword "slides" and the references cited at this point referenced.

• A.) 50,0 bis 99,99 Gewichtsteilen mindestens eines Polymers (A) und
• B.) 0,01 bis 50,0 Gewichtsteilen mindestens einer Hydroxyverbindung (B)
• C.) mit mindestens einer Verbindung (C) der Formel (5) umsetzt.

According to the invention, the coating has, based on its total weight, more than 0.1% by weight, preferably more than 0.5% by weight, advantageously more than 1.0% by weight, in particular more than 2.0% by weight. , at least one polyvinyl acetal (I) obtainable by a process comprising reacting a mixture of

• A.) 50.0 to 99.99 parts by weight of at least one polymer (A) and
• B.) 0.01 to 50.0 parts by weight of at least one hydroxy compound (B)
• C.) with at least one compound (C) of the formula (5).

there gives the sum of the parts by weight of A.) and B.) preferably 100.0 parts by weight.

• a.) 1,0 bis 99,9 Gew.-% Struktureinheiten der Formel (1)
  
• b.) 0 bis 99,0 Gew.-% Struktureinheiten der Formel (2)
  
• c.) 0,01 bis 70,0 Gew.-%, Struktureinheiten der Formel (3)
  

The polymer (A) contains in each case based on its total weight

• a.) 1.0 to 99.9% by weight of structural units of the formula (1)
  
• b.) 0 to 99.0% by weight of structural units of the formula (2)
  
• c.) 0.01 to 70.0% by weight, structural units of the formula (3)
  

there of course, the respective structural units are different from each other, In particular, in the context of the present invention, the structural unit comprises of the formula (3) does not have the structural units of the formula (1) or (2).

The radical R ¹ is in each case independently of one another hydrogen or methyl, preferably hydrogen.

The radical R ² denotes hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably an alkyl radical having 1 to 6 carbon atoms, suitably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl , tert-butyl, n-pentyl or an n-hexyl group, advantageously a methyl or an ethyl group, in particular a methyl group.

The radicals R ³ , R ⁴ , R ⁵ and R ⁶ are each independently radicals having a molecular weight in the range of 1 to 500 g / mol, suitably hydrogen, an optionally branched, aliphatic or cycloaliphatic radical having 1 to 16 carbon atoms, optionally may contain one or more carboxylic acid, carboxylic anhydride, carboxylic acid ester, carboxylic acid amide and / or sulfonic acid groups.

Particularly preferred structural units of the formula (3) are derived from straight-chain or branched olefins having 2 to 18 carbon atoms, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, (meth) acrylamides and / or ethylene sulfonic acid. In this case, olefins, in particular sol have a terminal CC double bond, preferably having 2 to 6 carbon atoms, in particular ethylene, proved to be particularly favorable. Furthermore, structural units (3) derived from acrylamidopropenylsulfonic acid (AMPS) also lead to very particularly advantageous results according to the invention.

The Total number of structural units of the formula (2) is preferable in the range of 0.1 to 40 mol%, suitably in the range of 0.5 to 25.0 mol%, in particular in the range of 1.0 to 15.0 mol%, in each case based on the total number of structural units of the formula (1 and 2). It is in accordance with a first preferred embodiment the present invention uses a polymer (A), which based on the total number of structural units of the formulas (1) and (2) Contains 1.0 to 2.0 mol% of structural units of the formula (2). According to one second preferred embodiment The present invention uses a polymer (A) which based on the total number of structural units of the formula (1) and (2) 3.0 to 7.0 mol% Structural units of the formula (2) contains. According to a third preferred Embodiment of Present invention, a polymer (A) is used, which based on the total number of structural units of the formulas (1) and (2) Contains 10.0 to 15.0 mol% of structural units of the formula (2).

According to one another particularly preferred embodiment of the present invention Invention contains this Polymer (A), in each case based on its total weight,> 50.0 wt .-%, advantageously> 60.0 wt .-%, advantageously> 70.0 wt .-%, in particular> 80.0 wt .-% of structural units of the formula (1) and / or (2). Particularly advantageous results can thereby be achieved with polymers (A), which, in each case based on their total weight,> 85.0 wt .-%, advantageously> 90.0 wt .-%, advantageously> 95.0 wt .-%, in particular> 99.0 Wt .-% of structural units of the formula (1) and / or (2).

in the Within the scope of the present invention, the polymer (A) may be a syndiotactic, possessing isotactic and / or atactic chain construction. Farther it may be present both as a random and as a block copolymer.

The viscosity of the polymer (A) is of minor importance according to the invention, in principle can Both low molecular weight and high molecular weight polymers (A) used become. Nevertheless, it is within the scope of the present invention as very cheap the polymer (A) has a viscosity in the range from 1 to 70 mPas, preferably in the range of 2 to 40 mPas, in particular in the range of From 3 to 30 mPas (measured as 4% strength by weight aqueous solution after Hoppler at 20 ° C, DIN 53015).

The Preparation of the invention to be used Polymers (A) can be prepared in a manner known per se in a two-stage Procedure done. In a first step, the corresponding Vinyl ester in a suitable solvent, usually water or an alcohol, such as methanol, ethanol, propanol and / or Butanol, using a suitable radical initiator, radically polymerized. Will the polymerization in the presence of radical carried out copolymerizable monomers, we obtain the corresponding vinyl ester copolymers.

The Vinyl ester (co) polymer is then in a second step, usually by transesterification with methanol, saponified, taking the saponification degree in a manner known per se, for example by varying the catalyst concentration, set the reaction temperature and / or the reaction time, targeted can. For more details will be on the standard Specialist literature, in particular Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-Rom Wiley-VCH, 1997, Keyword: Poly (Vinyl Acetals) and the references cited therein.

The Hydroxy compound (B) is sufficient according to the formula (4)

The radical R ⁷ denotes hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-butyl Pentyl or an n-hexyl group, in particular a methyl group. In a very particularly preferred embodiment of the present invention, the radical R ^{7 is} hydrogen.

In this case, the radicals R ^{7 can} each be selected independently of one another, ie each repeating unit -CHR ⁷ -CH ₂ -O- can have a different radical R ⁷ . Thus, the above definition of the hydroxy compound (B) includes both polyethylene glycol (monoether) and polypropylene glycol (monoether) and polyethylene glycol-co-propylene glycol (monoether). The latter can have both a statistical and a block-like structure, such as the polymers Pluronic ^® and Genapol ^®.

The radical R ⁸ denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, preferably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl; n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or an n-decyl group, especially a methyl group. According to a very particularly preferred embodiment of the present invention, the radical R ^{8 is} hydrogen.

n is a number greater than or equal 2, preferably a number in the range of 2 to 1000, conveniently in Range from 3 to 300, advantageously in the range of 3 and 25, particularly preferably in the range from 3 to 10, in particular in the range from 4 to 6. Furthermore can especially cheap Results are obtained when n is a number in the range of 10 to 20, in particular in the range of 12 to 15.

The Compound (C) according to the invention has the formula (5)

The radicals R ⁹ and R ¹⁰ are each independently hydrogen, COOH, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. These alkyl and aryl radicals may be substituted by one or more carboxyl, hydroxyl, sulfonic acid groups and / or halogen atoms, such as fluorine, chlorine, bromine, iodine. Preferred compounds (C) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethoxybutyraldehyde, paraldehyde, 1,3,5-trioxane, capronaldehyde, 2-ethylhexanal, pelargonaldehyde, 3,5,5- Trimethylhexanal, 2-formyl-benzo-sulfonic acid, acetone, ethyl methyl ketone, butyl ethyl ketone and I or ethyl hexyl ketone. According to another preferred embodiment, glyoxylic acid HCO-COOH is used as compound (C).

In the context of the present invention, the use of aldehydes, ie compounds of formula (5) where R ⁹ = hydrogen and R ¹⁰ = hydrogen, a methyl, ethyl, n-propyl or an iso-Prapylgruppe, preferably of Formaldehyde and / or n-butyraldehyde, in particular of n-butyraldehyde, very particularly proven.

The Proportions of the starting compounds (A), (B) and (C) are according to the invention in such a way selected that per mole of hydroxyl groups containing the polymer (A) and the hydroxy compound (B) contained in total, 0.0005 to 0.5 mol of the compound (C) is used.

Furthermore For example, compounds (B) and (C) are preferably in a compound (C) / compound ratio (B) greater than or equal one used.

The Reaction of the starting compounds (A), (B) and (C) is preferably carried out in at least one inert solvent, the term "inert Solvent "for such solvent is not under the respective reaction conditions with the react in the reaction system present compounds. One in this Context particularly expedient solvent is water.

Farther you lead the reaction favorably in the presence of acidic catalysts. Suitable acids include both organic acids, such as acetic acid as well as mineral acids, such as Hydrochloric acid, sulfuric acid and / or nitric acid, whereby the use of hydrochloric acid, Sulfuric acid and / or nitric acid especially proven in the art Has. The implementation the reaction is preferably carried out in such a way that a mixture from the components (A) and (B) in aqueous solution, the compound (C) in this solution enters and subsequently the acidic catalyst is added dropwise. According to another preferred embodiment It has also proved favorable for the present invention a mixture of components (A) and (B) in aqueous solution to introduce the acid catalyst in this solution and then stir the Reaction by adding the compound (C) to start.

The reaction temperature can be varied over a wide range, but often the temperature is in the range of -20.0 ° C to 100.0 ° C, preferably in the range of 0.0 ° C to 80.0 ° C. The same applies to the pressure at which the implementation is completed. Thus, the reaction can take place both at low pressure and at overpressure. Preferably, however, it is carried out at atmospheric pressure. Although the reaction can also take place under air, it has proven favorable in the context of the present invention to carry out the reaction under a protective gas atmosphere, preferably nitrogen and / or argon, preferably with a low oxygen content.

The solubility the polyvinyl acetal (I) leaves over adjust the degree of acetalization. This decreases in the course of the reaction too, causing the solubility of the resulting product in the aqueous medium decreases. By shifting the hydrophilic-lipophilic balance (HLB) increasingly towards hydrophobic separates the product from the watery Phase, first visible through clouding the solution and finally through thorough Failed from the same. The "fully acetalized" end product is no more soluble in water. It is separated as a solid and after appropriate workup recovered as a pure product.

Reduced now the amount of compound (C), the reaction runs to the entire Consumption of the same. Depending on the amount used is the product completely water-soluble or shows a temperature-dependent cloud point with increasing acetalization, d. H. the solubility of the polymer in water is - at given temperature - of the height depending on the implementation. In this way, it is also possible to produce products that, although in the Synthesis from the aqueous Oil out the phase, by addition of organic solvents, z. As alcohols, such as ethanol, but are completely dissolved again can. These products are then only in this special, the HLB value the polymer adapted, mixture soluble. Made of it Films are then neither in pure water nor in organic solvent soluble.

alternative Methods of preparation of the polyvinyl acetals (I) will be apparent to those skilled in the art. For example, it is possible instead of the compound (C) use compounds which are among the selected Reaction conditions Release compounds (C). These include u. a. cyclic trimers of aldehydes and acetals of aldehydes or Ketones. Furthermore, it is of course also possible that Polymer (A) first by reaction with an appropriate amount of compound (C) partially acetalize, then mix in the hydroxy compound (B) and the resulting mixture with a further amount of compound (C) implement.

The Structure of polyvinyl acetals (I) at the present time not yet complete clarified. Nevertheless, the current results suggest that the hydroxy compound (B) is covalently bound to the polymer because it is - in contrast to conventional Plasticizers - not more of the polymer, for example by means of an extraction (z. B. by Soxhlet extraction), isolate. However, it goes without saying itself, that the teaching of the present invention is not limited to this Interpretation limited is.

The coatings according to the invention are ink-jet printable without any further aids however expediently with other components, in particular pigments, polymer dispersions, water-soluble Cobinders, cationizing agents, sizing agents, wet strength agents, Wetting agents, antistatic agents, shading colorants, dispersants, processed optical brighteners and biocides into formulations, which possible are well matched to the inkjet printer and associated inks and which are able, if possible exactly the desired Paper properties like smoothness, White, To reproduce paper and printing gloss.

• – Siliziumoxid und ihre Herstellungsformen (Kieselsäuren, Kieselgele, Kieselsole, in der Form gefällt, geliert, pyrogen, mit mehrwertigen Metallionen, insbesondere Aluminium, dotiert, kolloidal gelöst);
• – oberflächenvergrößerte Varianten von gefälltem Calciumcarbonat und Kaolin (insbesondere kalzinierte Sorten);
• – Aluminiumoxiden und -oxid hydraten;
• – Titandioxid;
• – Bentoniten;
• – Montmorilloniten und
• – basischem Magnesiumcarbonat.

The ink jet printable pigments include all types of:

• - Silicon oxide and its production forms (silicas, silica gels, silica sols, precipitated in the mold, gelled, pyrogenic, with polyvalent metal ions, in particular aluminum, doped, colloidally dissolved);
• - Surface enlarged variants of precipitated calcium carbonate and kaolin (especially calcined varieties);
• - Aluminum oxides and oxide hydrates;
• - titanium dioxide;
• - bentonites;
• - montmorillonites and
• Basic magnesium carbonate.

These are preferably with conventional Pigments such as kaolin, ground or precipitated calcium carbonate, talc, Zeolite and / or alumina blended. Also organic pigments such as polystyrene, polymethylmethacrylate and urea-formaldehyde polycondensates proved to be particularly favorable.

Even though the above-described polyvinyl acetals (I) as a binder for aqueous dispersions completely are particularly suitable, it may be appropriate in individual cases, to use other co-binders, for example, the pigment wetting or dispersion or to improve adhesion. In this case, binders (= Binder) according to the invention substances, the same or different substances combine, wherein the setting of the substances by physical drying of the aqueous Dispersion takes place. Therefore, within a particularly preferred embodiment at least one further co-binder of the present invention uses. Suitable co-binders include all for aqueous dispersions known binders, preferably organic binders, in particular Polyvinyl alcohols, cellulose ethers, gelatin, polyvinylpyrrolidones, Polyvinyl sulfates, polyacrylates, polyacrylamides, maleic acid-styrene copolymers and others water-soluble Polymers.

• – synthetische Polymerdispersionen auf Basis Styrol-Butadien, Styrol-Acrylat, Acrylat, Vinylacetat, Vinylacetat-Acrylat, Vinylacetat-Ethen, Urethan, gegebenenfalls modifiziert mit ethylenisch-ungesättigten Säuren und ihren Anhydriden, Acrylnitril, Acrylamiden und methylolierte Formen, welche anionisch, nichtionogen oder kationisch eingestellt sind;
• – herkömmliche, nichtmodifizierte Polyvinylalkohole mit allen erhältlichen Molekulargewichten und Hydrolysegraden, vorzugsweise im Bereich von 60 bis 100%, sowie solche, wie die eben beschriebenen, welche ethylenisch- ungesättigte Säuren, kationische Gruppierungen, wie z. B. quaternäre Ammoniumsalze, Amine enthalten;
• – teilacetalisierte Polyvinylacetale, insbesondere -butyrale mit allen erhältlichen Molekulargewichten, Hydrolysegraden, vorzugsweise im Bereich von 60 bis 100 sowie Acetalisierungsgraden, vorzugsweise im Bereich von 0,1 bis 25%;
• – abgebaute Stärken;
• – Gelatine;
• – Guar;
• – Galaktomannan;
• – Kasein;
• – Methyl-, Carboxymethyl- und Hydroxyethylcellulose;
• – Proteine;
• – Polyvinylpyrrolidon sowie deren Derivate in allen Ionizitäten.

Very particularly suitable cobinders according to the invention comprise:

• Synthetic polymer dispersions based on styrene-butadiene, styrene-acrylate, acrylate, vinyl acetate, vinyl acetate-acrylate, vinyl acetate-ethene, urethane optionally modified with ethylenically unsaturated acids and their anhydrides, acrylonitrile, acrylamides and methylolated forms which are anionic, nonionic or cationic;
• - conventional, unmodified polyvinyl alcohols with all available molecular weights and degrees of hydrolysis, preferably in the range of 60 to 100%, and those such as those just described which ethylenically unsaturated acids, cationic groups such. For example, quaternary ammonium salts, amines;
• Partially acetalized polyvinyl acetals, in particular butyrals with all available molecular weights, degrees of hydrolysis, preferably in the range of 60 to 100 and degrees of acetalization, preferably in the range of 0.1 to 25%;
• - degraded starches;
• - gelatin;
• - Guar;
• - galactomannan;
• - casein;
• Methyl, carboxymethyl and hydroxyethyl cellulose;
• - proteins;
• - Polyvinylpyrrolidone and their derivatives in all ionicities.

The Amounts of co-binder can depending on the application chosen arbitrarily become. Nevertheless, it has proved to be very particularly favorable according to the invention, that the proportion of all co-binder based on the total mass all binders used in the range of 0.1 to 95.0 wt .-%, preferably in the range of 0.1 to 80.0 wt .-%, suitably in the range of 0.1 to 60.0 wt .-%, in particular in the range of 0.1 to <50.0 Wt .-% is. Very particularly advantageous results can be achieved when the proportion of all co-binder based on the total mass all binders used in the range of 0.1 to 40.0 wt .-%, preferably in the range of 0.1 to 25.0 wt .-%, suitably in the range of 0.1 to 10.0 wt .-%, in particular in the range of 0.1 to 5.0 wt .-% is.

in the Frame of a further particularly preferred embodiment of the present invention Invention is proportion of all co-binder based on the total mass all binders used in the range of 50.0 to 95.0 wt .-%, preferably in the range of 70.0 and 95.0 wt .-%, suitably in the range of 80.0 to 95.0 wt .-%, in particular in the range of 90.0 and 95.0 wt .-%.

in the Frame of a third particularly preferred embodiment of the present invention Invention contains the Coating no co-binder.

• – wasserlösliche Polymerisate mit quaternären Ammoniumsalzen, insbesondere Poly(diallyldimethylammonium-chlorid); lineare oder verzweigtkettige tertiäre Amine und Polyamine;
• – quarternierte Poly(meth)acrylat-Harze;
• – Polyethenimin-Derivate;
• – Polyaluminiumhydroxichloride;
• – Aluminiumsulfat.

For the purposes of the present invention, particularly suitable cationizing agents include:

• - Water-soluble polymers with quaternary ammonium salts, in particular poly (diallyldimethylammonium chloride); linear or branched tertiary amines and polyamines;
• Quaternized poly (meth) acrylate resins;
• - polyethenimine derivatives;
• - Polyaluminiumhydroxichloride;
• - aluminum sulphate.

• – Harze auf Basis von verseiftem Kolophonium und verstärkte Typen; hydrophob eingestellte Styrol-Maleinsäureanhydrid-Kondensate und
• – Styrol-Acrylat-Dispersionen.

Furthermore, in the context of the present invention, the following sizing agents have proven to be particularly favorable:

• Resins based on saponified rosin and reinforced types; hydrophobically adjusted styrene-maleic anhydride condensates and
• - styrene-acrylate dispersions.

• – Harnstoff-Formaldehyd-, Melamin-Formal-dehyd-, Glyoxal-, Polyamin- und Polyamidoamin-Epichlorhydrin-Harze;
• – Glyoxal;
• – Ammonium- und Alkalizirconiumcarbonat;
• – Aziridin-Derivate und
• – Acetylchitosan.

Wet strength agents particularly suitable according to the invention comprise:

• Urea-formaldehyde, melamine-formaldehyde, glyoxal, polyamine and polyamidoamine-epichlorohydrin resins;
• - glyoxal;
• - ammonium and alkali zirconium carbonate;
• - Aziridine derivatives and
• - acetylchitosan.

• – Styrol-Maleinsäureanhydrid-Addukte;
• – gesättigte und ungesättigte Fettalkoholethersulfonate sowie ihre ethoxylierten Derivate;
• – Fettaminoxethylate;
• – Polyglycolether und -sulfonate von Alkanolen und Alkenolen;
• – Alkylpolyglycolether;
• – Ethenoxid-Propenoxid-Blockcopolymerisate;
• – Alkanphosphorsäureester und
• – Alkyltrimethylammoniumchlorid.

In the context of the present invention, wetting agents designate natural or synthetic substances which in solution reduce the surface tension of the solvent, preferably water, so that they penetrate the surfaces of solid bodies (eg textile fibers) and saturate and wet them while displacing the air can. The wetting power of the wetting agent is usually determined by the dipping net method (DIN 53901). For further details, reference is made to the usual specialist literature, for example to Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999 and references cited therein. For the purposes of the present invention, particularly suitable wetting agents are:

• Styrene-maleic anhydride adducts;
• Saturated and unsaturated fatty alcohol ether sulfonates and their ethoxylated derivatives;
• - fatty aminoxethylates;
• - polyglycol ethers and sulfonates of alkanols and alkenols;
• - alkyl polyglycol ether;
• - Ethene oxide propene oxide block copolymers;
• Alkane phosphoric acid esters and
• - alkyltrimethylammonium chloride.

• – Alkali-Polyacrylate;
• – Alkali- und Ammoniumpolyphosphate;
• – Alkalimaleinat und Alkaliphosphonat;

Dispersants, for the purposes of the present invention, denote substances which facilitate the dispersion of particles in a dispersion medium, by lowering the interfacial tension between the two components, thus causing wetting. Preferred dispersants include:

• - alkali polyacrylates;
• - alkali and ammonium polyphosphates;
• - Alkalimaleinate and Alkaliphosphonat;

there need in the context of the present invention, silica-based pigments usually no dispersants.

antistatic agents, Nuancierfarbmittel, optical brighteners and biocides are described for the Applications are not critical and are used as needed. you are known to the skilled person.

The Thickness of the coating according to the invention is of minor importance in the context of the present invention and can be chosen arbitrarily depending on the application. Nevertheless, have themselves for the purpose the present invention coatings with a thickness in the range from 0.1 to 100 μm very well proven.

in the Within the scope of the present invention, the coating materials be applied in a known per se to the base material. It has turned out for the purposes of the present invention have proven to be particularly favorable, first mix all coating materials together and to homogenize in this way and then preferably this mixture by blade, roller, glue or film press or a non-contact Application method, in particular jet order, curtain coating on to apply the base material.

is the base material is little networkable, this is how it becomes able to adhere and / or its wettability before application of the coating expediently elevated. Very particularly advantageous results can be used here a corona radiation, a primer application, a pigmented precursor or a Combination of these wetting and adhesion promoting process steps achieved become.

Possible fields of use of the coated material according to the invention are immediately apparent to the person skilled in the art. It is particularly suitable for all applications, in particular with polyvinyl acetals specially marked with polyvinyl butyrals, coated materials. A particularly preferred field of application of the coated material in the context of the present invention is its use as a printable medium in ink-jet printing. For further details on ink jet printing, see the commonly used literature, in particular Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-ROM, Wiley-VCH, 1997 - Keyword: Imaging Technology 2.1.3 Ink-Jet Printing and the references cited here directed.

The The following examples and comparative examples serve to illustrate of the present invention, without any limitation should. The polyvinyl alcohols used are according to the nomenclature used by Kuraray Specialties Europe GmbH described. The one mentioned in the type designation in the first place Number indicates the viscosity 4% aqueous solution at 20 ° C as a relative measure of the degree of polymerization the polyvinyl alcohol; the second number indicates the degree of hydrolysis (saponification degree) the type of underlying polyvinyl acetate (partially hydrolyzed and fully hydrolyzed polyvinyl alcohol types). The apply from the company Kuraray Specialties Europe GmbH Fluctuations in terms of the characteristics, that is, the viscosity may vary by ± 0.5 mPa s, the degree of hydrolysis have a fluctuation of ± 1 mol%.

I. Synthesis of Polymers

• – Viskosität nach Höppler (4 und 8 Gew.-%ige Lösung; DIN 53015)
• – Trübungspunkt
• – Fällungspunkte der 4 und der 8 Gew.-%igen Lösung
• – Glasübergangstemperatur mittels DSC, Mettler Toledo Star System, Heizrate 10 K/min, 2. Heizen

The polymers to be used according to the invention are obtained as follows: First, the respective polyvinyl alcohol is dissolved in E-water in a manner known per se. After cooling the solution at 40 ° C with stirring, the desired amount of the respective hydroxy compound (B) and the compound (C), usually butyraldehyde added. Then, at 25 ° C over a suitable period of time, for example a period of 120 minutes, the desired amount of hydrochloric acid, for example, 200 ml of 20 wt .-% hydrochloric acid for 1000 g Polyvinylakohol, added and then a suitable period of time, for example, 120 minutes, stirred , With 10 wt .-% sodium hydroxide solution is then adjusted to pH 7 to 8. The product obtained is usually characterized using the following methods:

• - Höppler viscosity (4 and 8% strength by weight solution, DIN 53015)
• - cloud point
• - Precipitation points of 4 and 8 wt .-% solution
• - Glass transition temperature by DSC, Mettler Toledo Star System, heating rate 10 K / min, 2. heating

II. Coating process

The non-pigment-containing and the pigment-containing coating formulations are knife-coated with a semi-automatic wire doctor blade onto 100 μm thick o-PET film whose free surface energy is adjusted to 38-40 mN / m by corona irradiation. The coated films are dried at 120 ° C in a convection oven. For applying the non-pigment-containing orders on paper in the same manner wire doctor are used; the paper orders are IR-dried and smoothed after the job. The pigment-containing coating formulations are knife-coated on paper using Bench Blade Coater and also IR-dried and smoothed. The paper used is a neutrally produced, starch-sized, wood-free base paper with 80 g / m ² basis weight.

III. Examination of coatings

The dried coatings or lines are cxi means of the ink jet printers Hewlett-Packard Deskjet ^® 870, 970 cxi and Epson Photo stylu ^® sample printed 750th All three inkjet printers have the original printing inks of the printer manufacturers, which - except for black - are based on water-soluble dyes. The black ink is manufactured on a color pigment basis and usually behaves differently than the colored inks; therefore, black is judged separately.

• I Folienglanz, Papierglanz Pigmentbindekraft (bei Anwesenheit von Pigment) Adhäsionskraft mittels Tesatest (nur Folie; bei Abwesenheit von Pigment)
• II Intensität der Farben im vollflächigen Druck Homogenität der Farben im vollflächigen Druck Druckschärfe der Farben Ineinanderlaufen der Farben (bleeding) Druckfarbenglanz der Farben Trocknungsgeschwindigkeit der Farben Wasserfestigkeit der Farben
• III Intensität des Schwarzes im vollflächigen Druck Homogenität des Schwarzes im vollflächigen Druck Druckschärfe des Schwarzes Ineinanderlaufen des Schwarzes und der Farben (bleeding) Druckfarbenglanz des Schwarzes Trocknungsgeschwindigkeit des Schwarzes Wasserfestigkeit des Schwarzes

The self-designed test image is designed so that the following properties can be tested:

• I Film gloss, paper gloss Pigment binding force (in the presence of pigment) Adhesive strength by means of Tesatest (foil only, in the absence of pigment)
• II Intensity of colors in full-surface printing Homogeneity of colors in full-surface printing Sharpness of colors Coloring of colors (bleeding) Ink gloss of colors Color drying rate Water resistance of colors
• III Intensity of black in full-surface printing Homogeneity of black in full-surface printing Sharpness of black Blending of black and colors (bleeding) Ink gloss of black Drying speed of black Water resistance of black

The Test image contains narrow, juxtaposed strips of primary colors and of Black, which were arranged in the printing direction. For investigation The drying rate is using a cotton swab, directly After the streaks appear from the printer, the ink drying periodically checked and measured the time to its drying.

The Pigment binding force with silica is achieved by vigorous rubbing with the finger tested and graded. The adhesion is tested by demolishing a pressed-on Tesastreifens.

Around to achieve a good water resistance of the inkjet printing, it is necessary to vary the formulation specifically; she will therefore not always tested. For The water resistance test is printed with color and black Paper or foil pieces put into water and measured the time until the massive water attack.

All not expressly mentioned Properties of the above list are by comparison with each other assessed visually. The visual assessment has the throughput of large quantities from trial prints opposite The measurement methodology has the advantage that it is faster that you can Save the time-consuming determination of the error width of measuring instruments and that one can expect unexpected, metrologically elusive errors in the Pressure such as As the bad wetting, bronzing or Krakelieren sees immediately and can arrange correctly.

Either the measured values as well as the visual assessments are graded. The grading scheme is - according to the school grading system - as follows:

Table 1: Evaluation scheme

A. Non-pigmented ink jet printable coatings on foil

It be the following examples of the invention B1 to B5 and Comparative Examples VB1 to VB3, which by reaction the specified components available are examined (data in% by weight):

Table 2: investigated polyvinyl alcohols and polyvinyl acetals

The used polyvinyl alcohols can be characterized as follows:

Table 3: Characterization of polyvinyl alcohols

4-5 g / m ^{2 of} the polymers listed in Table 1 are applied by doctor blade on o-PET film and dried. No further additives are added. The results after printing with an Epson ^Stylus® Photo 750 are summarized in Tables 4a, 4b and 4c.

Table 4a: Printing results (general)

Table 4b: Printing results (color printing)

Table 4c: Printing results (black)

B Non-pigmented inkjet printable coatings on paper

It be the following examples of the invention B6 and Comparative Examples VB4 to VB7, which by reaction of the specified components available are examined (data in% by weight):

Table 5: investigated polyvinyl alcohols and polyvinyl acetel

The used polyvinyl alcohols can be characterized as follows:

Table 6: Characterization of polyvinyl alcohols

Tabelle 7b: Druckergebnisse (Schwarz; 2 g/m²)

Tabelle 7c: Druckergebnisse (Farbdruck; 6 g/m²)

Tabelle 7d: Druckergebnisse (Schwarz; 6 g/m²)

C. Silica-enthaltende tintenstrahlbedruckbare Striche auf Folie

werden hergestellt. Es werden folgende erfindungsgemäßen Beispiele B7 bis B10 und Vergleichsbeispiele VB8 bis VB11, welche durch Umsetzung der angegebenen Komponenten erhältlich sind, untersucht (Angaben in Gewichts%):100 parts by weight (dry) of the polymers from Table 5 are mixed with in each case one part by weight (dry) of polydiallyl-dimethylammonium chloride, and a) 2 g / m ² or b) 6 g / m ^{2 are spread} on base paper. Thereafter, the papers are dried, smoothed and conditioned at 23 ° C and 50% relative humidity. The results after printing on a Hewlett-Packard Deskjet ^® 870 cxi are summarized in Table 7a, 7b, 7c and 7d. Table 7a: Printing results (color printing, 2 g / m ² )

Table 7b: Printing results (black, 2 g / m ² )

Table 7c: Printing results (color printing, 6 g / m ² )

Table 7d: Printing results (black, 6 g / m ² )

C. Silica-containing inkjet printable lines on foil

are produced. The following Examples B7 to B10 according to the invention and Comparative Examples VB8 to VB11, which are obtainable by reacting the specified components, are investigated (data in% by weight):

Table 8: investigated polyvinyl acetals

The used polyvinyl alcohols can be characterized as follows:

Table 9: Characterization of polyvinyl alcohols

6 g / m ² of the coating color n which are added to those listed in Table 8, polymers corresponding to the above starting formulation, be applied by means of doctor blade unit on o-PET films and dried: The results after printing with a Hewlett Packard Deskjet ^® 970 cxi be in Tables 10a, 10b and 10c summarized.

Table 10a: Printing results (general)

Table 10b: Printing results (color printing)

Table 10c: Printing results (black)

Claims (17)

Coated inkjet printing material, characterized in that the coating contains more than 0.1% by weight, based on its total weight, of at least one polyvinyl acetal (I) obtainable by a process comprising a mixture of A.) 50, 0 to 99.99 parts by weight of at least one polymer (A) which contains a) 1.0 to 99.9% by weight of structural units of the formula (1)

where R ^{1 is} hydrogen or methyl, b.) 0 to 99.0% by weight of structural units of the formula (2)

where R ^{2 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, c.) 0.01 to 70.0% by weight of structural units of the formula (3)

wherein R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently radicals having a molecular weight in the range of 1 to 500 g / mol, each based on the total weight of the polymer (A), and B.) 0.01 to 50.0 parts by weight of at least one hydroxy compound (B) of the formula (4)

wherein R ⁷ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, R ^{8 is} hydrogen or an alkyl group having 1 to 10 carbon atoms and n is a number greater than or equal to 2, with C.) at least one compound (C) of the formula (5) implements,

wherein R ⁹ and R ^{10 are} each independently hydrogen, COOH, an alkyl group of 1 to 10 carbon atoms or an optionally substituted aryl group of 6 to 12 carbon atoms, wherein per mole of hydroxyl groups containing the polymer (A) and the hydroxy compound (B) contained in total, 0.0005 to 0.5 mol of the compound (C) is used. Coated material according to claim 1, characterized in that that the polyvinyl acetal is obtainable by a process in which one Polymer (A), which based on the total number of structural units of the formula (1) and (2) 0.1 to 40.0 mol% of structural units of Formula (2) contains. Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which a polymer (A) is used which contains 0.01 to 70% by weight Structural units of the formula (3) containing olefins containing 2 to 18 carbon atoms, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic, Derive (meth) acrylamides and / or ethylene sulfonic acid. Coated material according to claim 3, characterized that the polyvinyl acetal is obtainable by a process in which one Polymer (A) containing structural units of the formula (3), which derived from ethylene. Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which one uses a hydroxy compound (B) in which n is a number in the range of 2 and 1000. Coated material according to at least one of the preceding claims, characterized in that the polyvinyl acetal is obtainable by a process in which a hydroxy compound (B) is used in which R ^{8 is} hydrogen. Coated material according to at least one of the preceding claims, characterized in that the polyvinyl acetal is obtainable by a process in which a hydroxy compound (B) of the formula (4)

used, ^wherein each R ⁷ is independently hydrogen or methyl. Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which at least one ethylene oxide-propylene oxide block copolymer used as hydroxy compound (B). Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethoxybutyraldehyde, caproaldehyde, 2-ethylhexanal, pelargonaldehyde, 3,5,5-trimethylhexanal, 2-formyl-benzoic acid, acetone, ethyl methyl ketone, Butyl ethyl ketone and / or Ethylhexylketon as compound (C) is used. Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which the compounds (B) and (C) are compounded in a molar ratio (C) / compound (B) greater than or equal to one uses. Coated material after at least one of previous claims, characterized in that the polyvinyl acetal is obtained by a process available in which one is the reaction in the presence of acidic catalysts performs. Coated material after at least one of previous claims, characterized in that the coating is 0.1 to 100 microns thick. Coated material after at least one of previous claims, characterized in that the coated material based on its total weight of at least 50% by weight of paper, paperboard, textiles, Plastic films, aluminum or laminated laminates or Extrudates consists of these materials. Coated material after at least one of previous claims, characterized in that the coated material is a film which, based on their total weight, is more than 50% by weight of polyethylene, Polypropylene, polyester, polyvinyl chloride, polyacrylate, polymethacrylate and / or polycarbonate. Coated material after at least one of previous claims, characterized in that the coating further comprises an or several pigments, polymer dispersions, water-soluble co-binders, cationizing agents, Sizing agents, wet strength agents, wetting agents, antistatic agents, shading colorants, Dispersing agent, optical brightener and / or biocides. Process for producing a coated material according to at least one of the preceding claims, characterized in that a formulation containing at least a polyvinyl acetal (I) by means of a doctor blade, roller, glue or film press or a non-contact Application method applied to the material. Method according to claim 16, characterized in that that one has the adhesiveness and / or the wettability of the material before application of the Formulation increased.