EP0537633B1 - Method for treatment of grained and anodised lithographic printing plates and lithographic printing plates produced according to this method - Google Patents

Method for treatment of grained and anodised lithographic printing plates and lithographic printing plates produced according to this method Download PDF

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Publication number
EP0537633B1
EP0537633B1 EP92117258A EP92117258A EP0537633B1 EP 0537633 B1 EP0537633 B1 EP 0537633B1 EP 92117258 A EP92117258 A EP 92117258A EP 92117258 A EP92117258 A EP 92117258A EP 0537633 B1 EP0537633 B1 EP 0537633B1
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EP
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Prior art keywords
printing plate
process according
litho printing
salt solution
solution
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EP92117258A
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German (de)
French (fr)
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EP0537633A1 (en
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Andreas Dr. Elsässer
Michael Dr. Brenk
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer

Definitions

  • the invention relates to a method for treating roughened and anodized planographic printing plates to reduce the degradation of the metal oxide layer that forms during the anodizing, and planographic printing plates produced thereafter.
  • EP-A 0 069 320 discloses a method for producing offset printing plates whose carrier material is chemically-mechanically and / or electrochemically roughened aluminum or one of its alloys, the aluminum having an aluminum oxide layer produced by anodic oxidation.
  • a hydrophilic coating composed of at least one salt-like hydrophilic organic polymer, which is a complex reaction product of a) a water-soluble organic polymer with functional groups containing acidic phosphorus or sulfur, e.g. Is polyvinylphosphonic or polyvinylsulfonic acid and b) a salt of an at least divalent metal cation.
  • hydrophilization by such a complex reaction product of components a) and b) can also be carried out directly on the support material by immersing it successively in an aqueous solution of component a) and an aqueous solution of component b). After the hydrophilization, a radiation or photosensitive layer is applied in this process.
  • EP-A 0 218 160 describes a carrier material for a lithographic printing plate made of anodized aluminum, which has an anodizing layer, a silicate layer in contact with the anodizing layer and a metal salt layer carries, which in turn is in contact with the silicate layer.
  • the metal salt layer consists of a metal salt of the formula MX, in which M is a metal selected from the group consisting of zinc, magnesium, nickel and chromium and X is an anion selected from the group consisting of acetate, Chloride and borate.
  • the method for producing the carrier material comprises the steps of contacting an anodized aluminum plate with a silicate material and contacting the siliconized plate with the metal salt mentioned above.
  • Ribbons, plates or foils can be used for the aluminum supports of the presensitized planographic printing plates, which are provided with positive or negative working radiation-sensitive coatings.
  • these coatings contain polymers with functional units which ensure the development of the coatings in the aqueous alkaline developer solutions after imagewise exposure and, if appropriate, further processing steps, such as tempering or concreting.
  • functional units are -COOH, -SO 3 H, -PO 3 H 2 , -SH, -OH and -NH 2 .
  • the developer solutions generally contain alkali silicates as alkaline components.
  • Silicates have the advantage that they attack the Al 2 O 3 layer of the carrier surface built up in the anodizing step significantly less than other alkaline agents.
  • the object of the invention is to improve a method of the type described in the introduction in such a way that the degradation of the oxide coating on the front and back of the aluminum support and the resulting contamination of the printing forms and of the developing devices are avoided or effectively reduced.
  • a method for treating roughened and anodized planographic printing plates to reduce the degradation of the metal oxide layer that forms during the anodizing comprises the successive steps of hydrophilizing the planographic printing plate with polyvinylphosphonic acid and treating the hydrophilized planographic printing plate with a Saline solution of divalent or multivalent cations, which has a concentration of at least 0.02 mol / l, the salt solution being a salt from the group MgCl 2 , Mg (NO 3 ) 2 , CaCl 2 , Ca (NO 3 ) 2 , Ca acetate, SrCl 2 , Sr levulinate, BaCl 2 , Ba (NO 3 ) 2 , ScCl 3 , Sc 2 (SO 4 ) 3 , LaCl 3 , La (NO 3) 3 , TiCl 3 , VSO 4 , CrCl 2 Contains, MnBr 2 , NiCl 2 , CuCl 2 , Zn
  • the further development of the invention takes place through the process steps of coating the planographic printing plate with a radiation-sensitive layer, exposing this layer and developing the exposed layer with an aqueous alkaline solution.
  • Cation concentrations below 0.02 mol / l - such as those found in hard water - do not show sufficient effectiveness in improving the alkali stability of the anodized layer.
  • the preferred concentration range is between 0.04 and 0.4 mol / l.
  • the divalent or trivalent ions of the elements of the 2nd and 3rd main group and the 3rd subgroup of the periodic table are particularly suitable cations.
  • the divalent and trivalent cations of V, Cr, Mn, Fe, Co, Ni, Zn, Sn and Pb also show good effectiveness.
  • both inorganic and organic, mono- and polyvalent anions are suitable as anions, the choice being determined in particular by the solubility of the corresponding salts.
  • the treatment of the back of the aluminum support with the salt solution is preferably carried out at a temperature between 20 and 90 ° C in times between one second and one minute.
  • the salt solution is applied using the customary techniques, for example spraying, rinsing or dipping, the simplest way being after the hydrophilization of the front side and before applying the light-sensitive coating.
  • the backside can also be rinsed after the photosensitive coating has been applied. Drying after treatment with the salt solution at temperatures between 50 and 250 ° C can be advantageous.
  • planographic printing plates produced by the process according to the invention are characterized in that the aluminum support of the planographic printing plate is coated with a copy lacquer film and that the copy lacquer film is formed by drying a copy lacquer solution.
  • the design of further planographic printing plates according to the invention results from claims 16 to 19.
  • the advantage of the process and the planographic printing plates produced thereafter is that the treatment with the salt solution prevents the attack of the aqueous alkaline developer solution on the oxide layer on the front and back of the carrier material.
  • the copy varnish film is dried at 125 ° C for one minute.
  • the film weight is 1 to 3 g / m 2 , in particular 2.4 g / m 2 .
  • the presensitized planographic printing plates are processed into printing forms.
  • the plates are contacted in a vacuum contact copier frame by evacuation with a test pattern, exposed with a 5 kW metal halide-doped mercury vapor lamp at a distance of 110 cm so that an open step 4 results in the UGRA offset test wedge after development, which leads to high exposure Film edge removal corresponds.
  • the copy lacquer film is dried at 125 ° C. for 1 minute.
  • the film weight is 1.8 g / m 2 .
  • a potassium silicate developer according to DE-A 40 27 299 with a total alkali content of 1.3 mol / l and a content of polyglycol-1000-dicarboxylic acid of 0.6% by weight is used for the development.
  • the copy lacquer film is dried for two minutes at 125 ° C. and has a layer weight of 3.0 g / m 2 .
  • the barrier layer After drying for 1 minute at 125 ° C, the barrier layer has a layer weight of 2.0 g / m 2 .
  • the presensitized planographic printing plates thus obtained are exposed as in the examples under item 1) for 35 s and then in a developing device as in the examples under item 1) with an upstream demineralized water rinse of the front to remove the PVAl cover layer at a processing speed of Developed 0.6 m / min in a potassium silicate developer with a total alkali content of 0.55 mol / l and a nonionic wetting agent content (coconut fatty alcohol polyoxyethylene ether with about 8 oxyethylene units (Genapol C080 from Hoechst AG)) of 1 g / l .
  • Example 3-7 a thick and then a light coating on the squeeze rollers is shown, while in Example 3-3 no coating is visible.
  • the layers are dried at 125 ° C. for two minutes and have a layer weight of 5 g / m 2 .
  • planographic printing plates produced in this way which work according to the electrophotographic principle, are charged in the dark with a corona to -500 V, exposed in projection with 8 halogen lamps with 500 watts each for 30 s.
  • the resulting latent charge image is reinforced with a commercially available toner / carrier mixture using a magnetic roller. After heat-fixing the toner, the non-image areas are removed with the following solution: Na 2 SiO 3 2.0% by weight NaOH 0.2% by weight Ethylene glycol 15.0% by weight n-propanol 10.0% by weight

Description

Die Erfindung betrifft ein Verfahren zur Behandlung von aufgerauhten und anodisierten Flachdruckplatten zur Reduktion des Abbaus der Metalloxidschicht, die sich während der Anodisierung ausbildet, und danach hergestellte Flachdruckplatten.The invention relates to a method for treating roughened and anodized planographic printing plates to reduce the degradation of the metal oxide layer that forms during the anodizing, and planographic printing plates produced thereafter.

Aus der EP-A 0 069 320 ist ein Verfahren zur Herstellung von Offset-Druckplatten bekannt, deren Trägermaterial chemisch-mechanisch und/oder elektrochemisch aufgerauhtes Aluminium oder eine seiner Legierungen ist, wobei das Aluminium eine durch anodische Oxidation erzeugte Aluminiumoxidschicht aufweist. Auf einer der beider Oberflächen des Trägermaterials befindet sich eine hydrophile Beschichtung aus mindestens einem salzartigen hydrophilen organischen Polymeren, das ein komplexartiges Umsetzungsprodukt aus a) einem wasserlöslichen organischen Polymeren mit sauren Phosphor oder Schwefel enthaltenden funktionellen Gruppen, wie z.B. Polyvinylphosphon- oder Polyvinylsulfonsäure und b) einem Salz eines mindestens zweiwertigen Metallkations ist. Die Hydrophilierung durch ein derartiges komplexartiges Umsetzungsprodukt aus den Komponenten a) und b) kann auch unmittelbar auf dem Trägermaterial erfolgen, indem dieses nacheinander in eine wäßrige Lösung der Komponente a) und eine-wäßrige Lösung der Komponente b) getaucht wird. Nach der Hydrophilierung erfolgt bei diesem Verfahren das Aufbringen einer strahlungs- bzw. fotoempfindlichen Schicht.EP-A 0 069 320 discloses a method for producing offset printing plates whose carrier material is chemically-mechanically and / or electrochemically roughened aluminum or one of its alloys, the aluminum having an aluminum oxide layer produced by anodic oxidation. On one of the two surfaces of the carrier material there is a hydrophilic coating composed of at least one salt-like hydrophilic organic polymer, which is a complex reaction product of a) a water-soluble organic polymer with functional groups containing acidic phosphorus or sulfur, e.g. Is polyvinylphosphonic or polyvinylsulfonic acid and b) a salt of an at least divalent metal cation. The hydrophilization by such a complex reaction product of components a) and b) can also be carried out directly on the support material by immersing it successively in an aqueous solution of component a) and an aqueous solution of component b). After the hydrophilization, a radiation or photosensitive layer is applied in this process.

In der EP-A 0 218 160 ist ein Trägermaterial für eine lithografische Druckplatte aus anodisiertem Aluminium beschrieben, die eine Anodisierschicht, eine Silikatschicht in Kontakt mit der Anodisierschicht und eine Metallsalzschicht trägt, die wiederum in Kontakt mit der Silikatschicht ist. Die Metallsalzschicht besteht aus einem Metallsalz der Formel MX, in der M ein Metall ist, das aus der Gruppe ausgewählt wird, die aus Zink, Magnesium, Nickel und Chrom besteht, und X ein Anion ist, ausgewählt aus der Gruppe, bestehend aus Acetat, Chlorid und Borat. Das Verfahren zur Herstellung des Trägermaterials umfaßt die Schritte des Kontaktierens einer anodisierten Aluminiumplatte mit einem Silikatmaterial und die Kontaktierung der silikatisierten Platte mit dem voranstehend erwähnten Metallsalz.EP-A 0 218 160 describes a carrier material for a lithographic printing plate made of anodized aluminum, which has an anodizing layer, a silicate layer in contact with the anodizing layer and a metal salt layer carries, which in turn is in contact with the silicate layer. The metal salt layer consists of a metal salt of the formula MX, in which M is a metal selected from the group consisting of zinc, magnesium, nickel and chromium and X is an anion selected from the group consisting of acetate, Chloride and borate. The method for producing the carrier material comprises the steps of contacting an anodized aluminum plate with a silicate material and contacting the siliconized plate with the metal salt mentioned above.

Für die Aluminiumträger der vorsensibilisierten Flachdruckplatten können Bänder, Platten oder Folien verwendet werden, die mit positiv oder negativ arbeitenden strahlungsempfindlichen Beschichtungen versehen sind.Ribbons, plates or foils can be used for the aluminum supports of the presensitized planographic printing plates, which are provided with positive or negative working radiation-sensitive coatings.

Folgende strahlungsempfindliche Beschichtungen werden üblicherweise hierfür eingesetzt:

  • positiv oder negativ arbeitende Diazoverbindungen,
  • negativ arbeitende Mischungen aus olefinisch ungesättigten Verbindungen und Photoinitiatoren und
  • positiv arbeitende Mischungen mit Fotohalbleitern.
The following radiation-sensitive coatings are usually used for this:
  • positive or negative working diazo compounds,
  • Negative working mixtures of olefinically unsaturated compounds and photoinitiators and
  • positive working mixtures with photo semiconductors.

Als Filmbildner enthalten diese Beschichtungen Polymere mit funktionellen Einheiten, die die Entwicklung der Beschichtungen nach der bildmäßigen Belichtung und gegebenenfalls weiteren Verarbeitungsschritten, wie Temperung oder Betonerung, in den wäßrig-alkalischen Entwicklerlösungen sicherstellen. Beispiele solcher funktioneller Einheiten sind -COOH, -SO3H, -PO3H2, -SH, -OH und -NH2.As film formers, these coatings contain polymers with functional units which ensure the development of the coatings in the aqueous alkaline developer solutions after imagewise exposure and, if appropriate, further processing steps, such as tempering or concreting. Examples of such functional units are -COOH, -SO 3 H, -PO 3 H 2 , -SH, -OH and -NH 2 .

Als alkalische Komponenten enthalten die Entwicklerlösungen neben weiteren Inhaltsstoffen, wie Tensiden, Hydrotropen, Lösemitteln, Komplexbildnern etc., in der Regel Alkalisilikate. Silikate besitzen den Vorteil, daß sie die im Eloxierschritt aufgebaute Al2O3-Schicht der Trägeroberfläche deutlich weniger als andere alkalische Agenzien angreifen.In addition to other ingredients, such as surfactants, hydrotropes, solvents, complexing agents etc., the developer solutions generally contain alkali silicates as alkaline components. Silicates have the advantage that they attack the Al 2 O 3 layer of the carrier surface built up in the anodizing step significantly less than other alkaline agents.

Dennoch treten in der Praxis Probleme auf, und zwar insbesondere derart, daß das auf der Vorder- und Rückseite des Aluminiumträgers gebildete Al2O3 im Entwicklungsprozeß einem zum Teil starken Abbau unterliegt. Dabei entsteht insbesondere auf der Rückseite des Aluminiumträgers, die nur einen relativ dünnen Oxidbelag aufweist, ein gelartiger Belag, der sich auf den Abquetschwalzen der Entwicklungsgeräte ansammelt und von dort auf die entwickelten Flachdruckformen rückübertragen werden kann. Um die hieraus resultierenden Störungen im Druckprozeß zu vermeiden, ist es daher unvermeidlich, dieser Verschmutzung durch regelmäßige Reinigung der Entwicklungsgeräte vorzubeugen.Nevertheless, problems arise in practice, in particular in such a way that the Al 2 O 3 formed on the front and back of the aluminum carrier is subject to a strong degradation in the development process. In particular, on the back of the aluminum support, which has only a relatively thin oxide coating, a gel-like coating is formed, which accumulates on the squeeze rollers of the developing devices and can be transferred back from there to the developed planographic printing plates. In order to avoid the resulting malfunctions in the printing process, it is therefore inevitable to prevent this contamination by regular cleaning of the developing devices.

Aufgabe der Erfindung ist es, ein Verfahren der eingangs beschriebenen Art so zu verbessern, daß der Abbau des Oxidbelags auf der Vorder- und Rückseite des Aluminiumträgers und die dadurch bedingten Verschmutzungen der Druckformen sowie der Entwicklungsgeräte vermieden bzw. wirksam reduziert werden.The object of the invention is to improve a method of the type described in the introduction in such a way that the degradation of the oxide coating on the front and back of the aluminum support and the resulting contamination of the printing forms and of the developing devices are avoided or effectively reduced.

Diese Aufgabe wird durch ein Verfahren zur Behandlung von aufgerauhten und anodisierten Flachdruckplatten zur Reduktion des Abbaus der Metalloxidschicht, die sich während der Anodisierung ausbildet, in der Weise gelöst, daß das Verfahren die aufeinanderfolgenden Schritte Hydrophilierung der Flachdruckplatte mit Polyvinylphosphonsäure und Behandlung der hydrophilierten Flachdruckplatte mit einer Salzlösung aus zwei- oder mehrwertigen Kationen umfaßt, die eine Konzentration von mindestens 0,02 Mol/l aufweist, wobei die Salzlösung ein Salz aus der Gruppe MgCl2, Mg(NO3)2, CaCl2, Ca(NO3)2, Ca-Acetat, SrCl2, Sr-Lävulinat, BaCl2, Ba(NO3)2, ScCl3, Sc2(SO4)3, LaCl3, La(NO3)3, TiCl3, VSO4, CrCl2, MnBr2, NiCl2, CuCl2, ZnSO4, AlCl3, SnCl2 oder Pb-Acetat enthält.This object is achieved by a method for treating roughened and anodized planographic printing plates to reduce the degradation of the metal oxide layer that forms during the anodizing, in such a way that the method comprises the successive steps of hydrophilizing the planographic printing plate with polyvinylphosphonic acid and treating the hydrophilized planographic printing plate with a Saline solution of divalent or multivalent cations, which has a concentration of at least 0.02 mol / l, the salt solution being a salt from the group MgCl 2 , Mg (NO 3 ) 2 , CaCl 2 , Ca (NO 3 ) 2 , Ca acetate, SrCl 2 , Sr levulinate, BaCl 2 , Ba (NO 3 ) 2 , ScCl 3 , Sc 2 (SO 4 ) 3 , LaCl 3 , La (NO 3) 3 , TiCl 3 , VSO 4 , CrCl 2 Contains, MnBr 2 , NiCl 2 , CuCl 2 , ZnSO 4 , AlCl 3 , SnCl 2 or Pb acetate.

Die weitere Ausgestaltung der Erfindung geschieht durch die Verfahrensschritte Beschichten der Flachdruckplatte mit einer strahlungsempfindlichen Schicht, Belichten dieser Schicht und Entwickeln der belichteten Schicht mit einer wäßrig-alkalischen Lösung.The further development of the invention takes place through the process steps of coating the planographic printing plate with a radiation-sensitive layer, exposing this layer and developing the exposed layer with an aqueous alkaline solution.

Kationenkonzentrationen unterhalb von 0,02 mol/l - wie sie beispielsweise in hartem Wasser vorliegen - zeigen keine hinreichende Wirksamkeit in der Verbesserung der Alkalistabilität der Eloxalschicht. Der bevorzugte Konzentrationsbereich liegt zwischen 0,04 und 0,4 mol/l.Cation concentrations below 0.02 mol / l - such as those found in hard water - do not show sufficient effectiveness in improving the alkali stability of the anodized layer. The preferred concentration range is between 0.04 and 0.4 mol / l.

Als besonders geeignete Kationen sind die zwei- bzw. dreiwertigen Ionen der Elemente der 2. und 3. Hauptgruppe und der 3. Nebengruppe des Periodensystems zu nennen. Jedoch zeigen auch die zwei- bzw. dreiwertigen Kationen von V, Cr, Mn, Fe, Co, Ni, Zn, Sn und Pb eine gute Wirksamkeit.The divalent or trivalent ions of the elements of the 2nd and 3rd main group and the 3rd subgroup of the periodic table are particularly suitable cations. However, the divalent and trivalent cations of V, Cr, Mn, Fe, Co, Ni, Zn, Sn and Pb also show good effectiveness.

Als Anionen eignen sich grundsätzlich sowohl anorganische als auch organische, mono- wie polyvalente Anionen, wobei die Auswahl insbesondere von der Löslichkeit der entsprechenden Salze bestimmt wird.In principle, both inorganic and organic, mono- and polyvalent anions are suitable as anions, the choice being determined in particular by the solubility of the corresponding salts.

Die Behandlung der Rückseite des Aluminiumträgers mit der Salzlösung erfolgt bevorzugt bei einer Temperatur zwischen 20 und 90 °C in Zeiten zwischen einer Sekunde und einer Minute.The treatment of the back of the aluminum support with the salt solution is preferably carried out at a temperature between 20 and 90 ° C in times between one second and one minute.

Die Applizierung der Salzlösung erfolgt mittels der üblichen Techniken, z.B. Sprühen, Spülen oder Tauchen, am einfachsten nach der Hydrophilierung der Vorderseite und vor Aufbringung der lichtempfindlichen Beschichtung. Die Spülung der Rpückseite kann auch nach dem Aufbringen der lichtempfindlichen Beschichtung vorgenommen werden. Eine Trocknung nach der Behandlung mit der Salzlösung bei Temperaturen zwischen 50 und 250 °C kann vorteilhaft sein.The salt solution is applied using the customary techniques, for example spraying, rinsing or dipping, the simplest way being after the hydrophilization of the front side and before applying the light-sensitive coating. The backside can also be rinsed after the photosensitive coating has been applied. Drying after treatment with the salt solution at temperatures between 50 and 250 ° C can be advantageous.

Die weitere Ausgestaltung des Verfahrens ergibt sich aus den Verfahrensmaßnahmen der Ansprüche 11 bis 15.The further development of the method results from the procedural measures of claims 11 to 15.

Für die sonstigen Behandlungsschritte der Trägeroberfläche, wie Beizung, Aufrauhung, Zwischenbeizung und Eloxierung, ergeben sich in bezug auf den Stand der Technik keine weiteren Besonderheiten.For the other treatment steps of the carrier surface, such as pickling, roughening, intermediate pickling and anodizing, there are no further special features in relation to the prior art.

Die nach dem erfindungsgemäßen Verfahren hergestellten Flachdruckplatten zeichnen sich dadurch aus, daß der Aluminiumträger der Flachdruckplatte mit einem Kopierlackfilm beschichtet ist und daS der Kopierlackfilm durch Trocknen einer Kopierlacklösung gebildet wird. Die Ausgestaltung weiterer Flachdruckplatten nach der Erfindung ergibt sich aus den Ansprüchen 16 bis 19.The planographic printing plates produced by the process according to the invention are characterized in that the aluminum support of the planographic printing plate is coated with a copy lacquer film and that the copy lacquer film is formed by drying a copy lacquer solution. The design of further planographic printing plates according to the invention results from claims 16 to 19.

Der Vorteil des Verfahrens und der danach hergestellten Flachdruckformen liegt darin, daß durch die Behandlung mit der Salzlösung der Angriff der wäßrig-alkalischen Entwicklerlösung auf die Oxidschicht auf der Vorder- und Rückseite des Trägermaterials unterbunden, wird.The advantage of the process and the planographic printing plates produced thereafter is that the treatment with the salt solution prevents the attack of the aqueous alkaline developer solution on the oxide layer on the front and back of the carrier material.

Die nachfolgenden Beispiele erläutern im Detail den Gegenstand der Erfindung und sind den Verglelchsbeispielen gegenübergestellt.The following examples explain the subject matter of the invention in detail and are compared with the comparative examples.

1. Beispiele für die Behandlung der Oxidschicht nach der Hydrophilierung mit unterschiedlichen Salzlösungen bei gleicher Temperatur1. Examples of the treatment of the oxide layer after the hydrophilization with different salt solutions at the same temperature

Ein walzblankes Aluminiumband der Stärke 0,3 mm wird in NaOH gebeizt, in Salzsäure elektrolytisch aufgerauht (Rz-Wert nach DIN 4768: 5,0 µm), in Schwefelsäure eloxiert (Oxidgewicht auf der Vorderseite 4,0 g/m2, am Rand der Rückseite 1,7 g/m2, in der Mitte der Rückseite 0,3 g/m2) und mit Polyvinylphosphonsäurelösung entsprechend der DE-B 16 21 478 hydrophiliert. Danach wird das Aluminiumband mit verschiedenen 0,02 bis 0,4 molaren Salzlösungen (siehe Tabelle 1) 1 bis 60 s bei 20 bis 90 °C besprüht und dann mit einer Kopierlacklösung beschichtet, die folgende Bestandteile enthält:

  • a) ein Kresol-Formaldehyd-Novolakharz,
  • b) ein Veresterungsprodukt eines 1,2-Naphthochinon-2-diazid-4- oder - 5-sulfonylchlorids mit einem Phenolderivat,
  • c) eine bei Bestrahlung eine starke Säure bildendende Verbindung,
  • d) ein kationischer Farbstoff und
  • e) ein Lösemittel oder Lösemittelgemisch mit einem Siedepunkt kleiner 200 °C.
A bright rolled aluminum strip with a thickness of 0.3 mm is pickled in NaOH, electrolytically roughened in hydrochloric acid (Rz value according to DIN 4768: 5.0 µm), and anodized in sulfuric acid (Oxide weight 4.0 g / m 2 on the front, 1.7 g / m 2 at the edge of the back, 0.3 g / m 2 in the middle of the back) and hydrophilized with polyvinylphosphonic acid solution according to DE-B 16 21 478 . The aluminum strip is then sprayed with various 0.02 to 0.4 molar salt solutions (see Table 1) for 1 to 60 s at 20 to 90 ° C. and then coated with a copy lacquer solution which contains the following constituents:
  • a) a cresol-formaldehyde novolak resin,
  • b) an esterification product of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonyl chloride with a phenol derivative,
  • c) a compound which forms a strong acid when irradiated,
  • d) a cationic dye and
  • e) a solvent or solvent mixture with a boiling point less than 200 ° C.

In einem speziellen Ausführungsbeispiel enthält die Kopierlacklösung folgende Bestandteile:

5,00 Gew.-%
Kresol-Formaldehyd-Novolakharz mit einer Hydroxylzahl von 420 nach DIN 53783/53240 und einem Molekulargewicht (Mw) nach GPC von 10000 (Polystyrol-Standard),
1,20 Gew.-%
Veresterungsprodukt von 3 mol 1,2-Naphthochinon-2-diazid-5-sulfonyl-chlorid und 1 mol 2,3,4-Trihydroxy-benzophenon,
0,15 Gew.-%
1.2-Naphthochinon -2-dazid-4-sulfo-nylchlorid,
0,05 Gew.-%
Victoriareinblau (C.I. 44045) und
ad 100 Gew.-%
eines Lösemittelgemisches aus Methylethylketon und Propylenglykolmonomethylether (40/60).
In a special embodiment, the copy varnish solution contains the following components:
5.00% by weight
Cresol-formaldehyde novolak resin with a hydroxyl number of 420 according to DIN 53783/53240 and a molecular weight (Mw) according to GPC of 10,000 (polystyrene standard),
1.20% by weight
Esterification product of 3 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and 1 mol of 2,3,4-trihydroxy-benzophenone,
0.15% by weight
1,2-naphthoquinone -2-dazid-4-sulfonyl chloride,
0.05% by weight
Victoriareinblau (CI 44045) and
ad 100% by weight
a solvent mixture of methyl ethyl ketone and propylene glycol monomethyl ether (40/60).

Der Kopierlackfilm wird eine Minute lang bei 125 °C getrocknet. Das Filmgewicht beträgt 1 bis 3 g/m2, insbesondere 2,4 g/m2.The copy varnish film is dried at 125 ° C for one minute. The film weight is 1 to 3 g / m 2 , in particular 2.4 g / m 2 .

Die vorsensibilisierten Flachdruckplatten werden zu Druckformen verarbeitet. Die Platten werden in einem Vakuum-Kontaktkopierrahmen durch Evakuieren mit einem Testbild kontaktiert, mit einer 5-kW-metallhalogeniddotierten Quecksilberdampflampe im Abstand von 110 cm so belichtet, daß nach Entwicklung eine offene Stufe 4 im UGRA-Offset-Testkeil resultiert, was einer Hochbelichtung zur Filmkanteneliminierung entspricht.The presensitized planographic printing plates are processed into printing forms. The plates are contacted in a vacuum contact copier frame by evacuation with a test pattern, exposed with a 5 kW metal halide-doped mercury vapor lamp at a distance of 110 cm so that an open step 4 results in the UGRA offset test wedge after development, which leads to high exposure Film edge removal corresponds.

Danach wird eine Minute lang bei 25 °C in einem Entwicklungsgerät (VA 86 der Hoechst AG) mit einem Kaliumsilikat-Entwickler, der einen Gesamtalkaligehalt von 0,95 mol/l aufweist, entwickelt.Thereafter, development is carried out for one minute at 25 ° C. in a developing device (VA 86 from Hoechst AG) with a potassium silicate developer which has a total alkali content of 0.95 mol / l.

Es erfolgt eine Beurteilung durch Augenscheinnahme, inwieweit es beim Entwicklungsprozeß zu einem Abbau der Oxidschicht des Trägermaterials kommt. Visuell macht sich der Abbau in Form eines weißen, streifigen Belags auf der Rückseite des Trägermaterials bemerkbar.There is an assessment by eye to what extent the oxide layer of the carrier material degrades during the development process. The degradation is visually noticeable in the form of a white, streaky covering on the back of the carrier material.

Das Bewertungsschema in der nachfolgenden Tabelle 1 lautet wie folgt:

(+) =
starker Oxidabbau
(0) =
leichter Oxidabbau (d.h. vor allem im Randbereich der Rückseite)
(-) =
Oxidabbau nicht feststellbar
Tabelle 1 Beispiele Salz Bewertung 1- 1 MgCl2 - 1- 2 Mg(NO3)2 - 1- 3 CaCl2 - 1- 4 Ca(NO3)2 - 1- 5 Ca-Acetat - 1- 6 SrCl2 - 1- 7 Sr-Lävulinat - 1- 8 BaCl2 - 1- 9 Ba(NO3)2 - 1-10 ScCl3 - 1-11 Sc2(SO4)3 - 1-12 LaCl3 - 1-13 La(NO3)3 - 1-14 TiCl3 - 1-15 VSO4 - 1-16 CrCl2 - 1-17 MnBr2 - 1-18 NiCl2 - 1-19 CuCl2 - 1-20 ZnSO4 - 1-21 AlCl3 - 1-22 SnCl2 - 1-23 Pb-Acetat - Vergleichsbeispiele Salz Bewertung 1-24 ohne Spülung + 1-25 nur VE-Wasser + The evaluation scheme in Table 1 below is as follows:
(+) =
strong oxide degradation
(0) =
easy oxide degradation (ie especially in the edge area of the back)
(-) =
Oxide degradation not ascertainable
Table 1 Examples salt rating 1- 1 MgCl 2 - 1- 2 Mg (NO 3 ) 2 - 1- 3 CaCl 2 - 1- 4 Ca (NO 3 ) 2 - 1- 5 Ca acetate - 1- 6 SrCl 2 - 1- 7 Sr levulinate - 1- 8 BaCl 2 - 1- 9 Ba (NO 3 ) 2 - 1-10 ScCl 3 - 1-11 Sc 2 (SO 4 ) 3 - 1-12 LaCl 3 - 1-13 La (NO 3 ) 3 - 1-14 TiCl 3 - 1-15 VSO 4 - 1-16 CrCl 2 - 1-17 MnBr 2 - 1-18 NiCl 2 - 1-19 CuCl 2 - 1-20 ZnSO 4 - 1-21 AlCl 3 - 1-22 SnCl 2 - 1-23 Pb acetate - Comparative examples salt rating 1-24 without rinsing + 1-25 only demineralized water +

2. Beispiele für die Behandlung der Oxidschicht nach der Hydrophilierung mit der gleichen Salzlösung bei unterschiedlichen Temperaturen2. Examples of the treatment of the oxide layer after hydrophilization with the same salt solution at different temperatures

Eine in Salpetersäure elektrolytisch aufgerauhte (Rz-Wert nach DIN 4768: 3,2 µm), in Schwefelsäure eloxierte (Oxidgewicht auf der Vorderseite 2,0 g/m2, am Rand der Rückseite 1,2 g/m2, in der Mitte der Rückseite 0,2 g/m2) Aluminiumfolie der Stärke 0,3 mm wird mit Polyvinylphosphonsäure entsprechend der DE-B 16 21 478 hydrophiliert, 1 bis 60 s bei verschiedenen Temperaturen (siehe Tabelle 2) in eine Ca-Salzlösung mit mehr als 0,02 mol/l, z. B. in 0,15 molare CaCl2-Lösung, getaucht, 15 s bei 120 °C getrocknet und dann mit einer Kopierlacklösung beschichtet, die folgende Bestandteile enthält:

  • a) ein Kresol-Formaldehyd-Novolakharz,
  • b) ein Veresterungsprodukt eines 1,2-Naphthochinon-2-diazid-4- oder -5-sulfonylchlorids mit einem Phenolderivat,
  • c) eine bei Bestrahlung eine starke Säure bildendende Verbindung,
  • d) einen kationischen Farbstoff und
  • e) einen Kieselsäurefüllstoff mit einer mittleren Korngröße von 3 bis 5 µm,
  • f) ein Tensid auf Basis von Dimethylsiloxan- und Ethylenoxideinheiten und
  • g) ein Lösemittel oder Lösemittelgemisch mit einem Siedepunkt kleiner 200 °C.
An electrolytically roughened in nitric acid (Rz value according to DIN 4768: 3.2 µm), anodized in sulfuric acid (oxide weight on the front 2.0 g / m 2 , on the edge of the back 1.2 g / m 2 , in the middle the back 0.2 g / m 2 ) aluminum foil with a thickness of 0.3 mm is hydrophilized with polyvinylphosphonic acid according to DE-B 16 21 478, 1 to 60 s at different temperatures (see Table 2) in a Ca salt solution with more than 0.02 mol / l, e.g. B. in 0.15 molar CaCl 2 solution, dipped, dried for 15 s at 120 ° C. and then coated with a copy lacquer solution which contains the following constituents:
  • a) a cresol-formaldehyde novolak resin,
  • b) an esterification product of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonyl chloride with a phenol derivative,
  • c) a compound which forms a strong acid when irradiated,
  • d) a cationic dye and
  • e) a silica filler with an average grain size of 3 to 5 µm,
  • f) a surfactant based on dimethylsiloxane and ethylene oxide units and
  • g) a solvent or solvent mixture with a boiling point less than 200 ° C.

In einem speziellen Ausführungsbeispiel enthält die Kopierlacklösung folgende Bestandteile:

4,80 Gew.-%
Kresol-Formaldehyd-Novolakharz mit einer Hydroxylzahl von 420 nach DIN 53783/53240 und einem Molekulargewicht (Mw) nach GPC von 10000 (Polystyrol-Standard),
1,05 Gew.-%
Veresterungsprodukt von 3 mol 1,2-Naphthochinon-2-diazid-4-sulfonylchlorid und 1 mol 2,3,4-Trihydroxybenzophenon,
0,05 Gew.-%
2-(4-Styrylphenyl)-4,6-bis-trichlormethyl-s-triazin,
0,10 Gew.-%
Kristallviolett (C.I. 42555) und
1,00 Gew.-%
Kieselsäurefüllstoff mit einer mittleren Korngröße von 3,9 µm,
0,10 Gew.-%
Tensid auf Basis von Dimethylsiloxan- und Ethylenoxideinheiten,
ad 100 Gew.-%
eines Lösemittelgemisches aus Tetrahydrofuran und Propylenglykolmonomethylether (55/45).
In a special embodiment, the copy varnish solution contains the following components:
4.80% by weight
Cresol-formaldehyde novolak resin with a hydroxyl number of 420 according to DIN 53783/53240 and a molecular weight (Mw) according to GPC of 10,000 (polystyrene standard),
1.05% by weight
Esterification product of 3 mol of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1 mol of 2,3,4-trihydroxybenzophenone,
0.05% by weight
2- (4-styrylphenyl) -4,6-bis-trichloromethyl-s-triazine,
0.10% by weight
Crystal violet (CI 42555) and
1.00% by weight
Silica filler with an average grain size of 3.9 µm,
0.10% by weight
Surfactant based on dimethylsiloxane and ethylene oxide units,
ad 100% by weight
a solvent mixture of tetrahydrofuran and propylene glycol monomethyl ether (55/45).

Der Kopierlackfilm wird 1 Minute bei 125 °C getrocknet. Das Filmgewicht beträgt 1,8 g/m2.The copy lacquer film is dried at 125 ° C. for 1 minute. The film weight is 1.8 g / m 2 .

Die Verarbeitung der gefertigten Flachdruckplatten mit einer umkehrbaren Positivschicht geschieht folgendermaßen:

  • Belichtung in einem Kopierrahmen wie in den Beispielen unter Punkt 1) durch eine Testvorlage, 60 s lang,
  • 1-minütige Temperung bei 135 °C in einem Durchlaufofen,
  • Abkühlung durch Umluftkühlung, 10 s lang,
  • Ausbelichtung ohne Vorlage mit UV-A-Leuchtstofflampen einer Strahlungsleistung von 240 Watt, 30 s lang in einem Durchlaufgerät,
  • Entwicklung in einem Gerät wie in den Beispielen unter Punkt 1) bei einer Verarbeitungsgeschwindigkeit der Druckplatten von 0,5 m/min.
The processed planographic printing plates with a reversible positive layer are processed as follows:
  • Exposure in a copying frame as in the examples under point 1) through a test template, for 60 s,
  • 1-minute tempering at 135 ° C in a continuous furnace,
  • Cooling by forced air cooling, for 10 s,
  • Exposure without original with UV-A fluorescent lamps with a radiation power of 240 watts, for 30 s in a continuous flow device,
  • Development in a device as in the examples under point 1) at a processing speed of the printing plates of 0.5 m / min.

Zur Entwicklung wird ein Kaliumsilikat-Entwickler entsprechend der DE-A 40 27 299 mit einem Gesamtalkaligehalt von 1,3 mol/l und einem Gehalt an Polyglykol-1000-dicarbonsäure von 0,6 Gew.-% eingesetzt.A potassium silicate developer according to DE-A 40 27 299 with a total alkali content of 1.3 mol / l and a content of polyglycol-1000-dicarboxylic acid of 0.6% by weight is used for the development.

Untersucht wird neben dem Kriterium Oxidabbau, der wie in den Beispielen unter Punkt 1) bewertet wird, das kopiertechnische Verhalten, d.h. Lichtempfindlichkeit, Wiedergabe, Farbschleier, Unterstrahlungsanfälligkeit, und das drucktechnische Verhalten, d.h. Freilaufen, Wasserbedarf, Auflage, der so gefertigten Flachdruckplatten. Tabelle 2 Beispiele Temperatur in °C Oxidabbau Verhalten Kopie/Druck 2- 1 20 - keine Nachteile gegenüber Standard 2- 2 30 - " 2- 3 40 - " 2- 4 50 - " 2- 5 60 - " 2- 6 70 - " 2- 7 80 - " 2- 8 90 - " Vergleichsbeispiel 2- 9 ohne Spülung + Standard In addition to the criterion oxide degradation, which is evaluated as in the examples under point 1), the copying behavior, i.e. light sensitivity, reproduction, color fog, susceptibility to under-radiation, and the printing behavior, ie free running, water requirement, support, of the planographic printing plates produced in this way are examined. Table 2 Examples Temperature in ° C Oxide degradation Behavior copy / print 2- 1 20th - no disadvantages compared to standard 2- 2 30th - " 2-3 40 - " 2-4 50 - " 2- 5 60 - " 2- 6 70 - " 2- 7 80 - " 2- 8 90 - " Comparative example 2- 9 without rinsing + default

3. Beispiele für die Behandlung der Oxidschicht nach dem Aufbringen der strahlungsempfindlichen Schicht mit unterschiedlichen Konzentrationen der gleichen Salzlösung3. Examples of the treatment of the oxide layer after the application of the radiation-sensitive layer with different concentrations of the same salt solution

Ein gemäß den Beispielen unter Punkt 1) gefertigter Flachdruckplattenträger wird nach der Hydrophilierung mit einer Lösung beschichtet, die folgende Bestandteile enthält:

  • a) eine Verbindung mit mindestens einer olefinisch ungesättigten Doppelbindung,
  • b) ein polymeres, alkalilösliches Bindemittel mit einer Säurezahl größer 10,
  • c) einen Photoinitiator,
  • d) einen Farbstoff und
  • e) ein Lösemittel oder Lösemittelgemisch mit einem Siedepunkt kleiner 200 °C.
A planographic printing plate support manufactured according to the examples in point 1) is coated after the hydrophilization with a solution which contains the following constituents:
  • a) a compound with at least one olefinically unsaturated double bond,
  • b) a polymeric, alkali-soluble binder with an acid number greater than 10,
  • c) a photoinitiator,
  • d) a dye and
  • e) a solvent or solvent mixture with a boiling point less than 200 ° C.

In einem speziellen Ausführungsbeispiel enthält die Lösung folgende Bestandteile:

3,00 Gew.-%
Trimethylolpropantriacrylat,
10,00 Gew.-%
Copolymer aus Mehylmethacrylat und Methacrylsäure mit einer Säurezahl von 190 und einem Molekulargewicht (Mw) nach GPC von 50000 (Polystyrol-Standard),
0,05 Gew.-%
Dibenzalaceton,
0,05 Gew.-%
9-Phenylacridin,
0,10 Gew.-%
eines Azofarbstoffs aus 2,4-Dinitro-6-Chlor-Benzoldiazoniumchlorid und 2-Methoxy-5-Acetylamino-N-Cyanoethyl-N-Hydroxyethyl-Anilin und
ad 100 Gew.-%
Ethylenglykolmonomethylether.
In a special embodiment, the solution contains the following components:
3.00% by weight
Trimethylolpropane triacrylate,
10.00% by weight
Copolymer of methyl methacrylate and methacrylic acid with an acid number of 190 and a molecular weight (Mw) according to GPC of 50,000 (polystyrene standard),
0.05% by weight
Dibenzalacetone,
0.05% by weight
9-phenylacridine,
0.10% by weight
an azo dye of 2,4-dinitro-6-chloro-benzenediazonium chloride and 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethyl-aniline and
ad 100% by weight
Ethylene glycol monomethyl ether.

Der Kopierlackfilm wird zwei Minuten lang bei 125 °C getrocknet und besitzt ein Schichtgewicht von 3,0 g/m2.The copy lacquer film is dried for two minutes at 125 ° C. and has a layer weight of 3.0 g / m 2 .

Danach wird die Rückseite der Trägerfolie mit Ca-Salzlösungen, z. B. Ca(NO3)2-Lösungen verschiedener Konzentrationen (Tabelle 3), bei 20 bis 90 °C zwischen 1 und 60 s besprüht und dann auf die Vorderseite als SauerstoffNachdiffusionssperrschicht folgende Lösung aufgebracht:

2,20 Gew.-%
Polyvinylalkohol mit einem Restacetylgruppengehalt von 10,7 %, dessen 4%ige wäßrige Lösung eine Viskosität von 8 mPas besitzt (Mowiol 8-88 der Hoechst AG),
0,02 Gew.-%
sec. -Natrium-Alkansulfonat (Hostapur SAS der Hoechst AG),
0,02 Gew.-%
Chloracetamid und
ad 100 Gew.-%
VE-Wasser.
Then the back of the carrier film with Ca salt solutions, eg. B. Ca (NO 3 ) 2 solutions of various concentrations (Table 3), sprayed at 20 to 90 ° C for 1 to 60 s and then applied the following solution to the front as an oxygen rediffusion barrier layer:
2.20% by weight
Polyvinyl alcohol with a residual acetyl group content of 10.7%, the 4% aqueous solution of which has a viscosity of 8 mPas (Mowiol 8-88 from Hoechst AG),
0.02% by weight
sec. sodium alkanesulfonate (Hostapur SAS from Hoechst AG),
0.02% by weight
Chloroacetamide and
ad 100% by weight
VE water.

Nach 1-minütiger Trocknung bei 125 °C besitzt die Sperrschicht ein Schichtgewicht von 2,0 g/m2.After drying for 1 minute at 125 ° C, the barrier layer has a layer weight of 2.0 g / m 2 .

Die so erhaltenen vorsensibilisierten Flachdruckplatten werden wie in den Beispielen unter Punkt 1) 35 s belichtet und dann in einem Entwicklungsgerät wie in den Beispielen unter Punkt 1) mit einer vorgeschalteten VE-Wasser-Spülung der Vorderseite zur Entfernung der PVAl-Deckschicht bei einer Verarbeitungsgeschwindigkeit von 0,6 m/min in einem Kaliumsilikat-Entwickler mit einem Gesamtalkaligehalt von 0,55 mol/l und einem Gehalt an nichtionischem Netzmittel (Kokosfettalkohol-Polyoxyethylenether mit ca. 8 Oxyethyleneinheiten (Genapol C080 der Hoechst AG)) von 1 g/l entwickelt.The presensitized planographic printing plates thus obtained are exposed as in the examples under item 1) for 35 s and then in a developing device as in the examples under item 1) with an upstream demineralized water rinse of the front to remove the PVAl cover layer at a processing speed of Developed 0.6 m / min in a potassium silicate developer with a total alkali content of 0.55 mol / l and a nonionic wetting agent content (coconut fatty alcohol polyoxyethylene ether with about 8 oxyethylene units (Genapol C080 from Hoechst AG)) of 1 g / l .

Der Oxidabbau wird wiederum wie in den Beispielen unter Punkt 1) bewertet. Tabelle 3 Beispiele Salzkonzentration Oxidabbau 3-1 0,02 mol/l - 3-2 0,04 mol/l - 3-3 0,10 mol/1 - 3-4 0,20 mol/l - 3-5 0,40 mol/l - Vergleichsbeispiele 3-6 ohne Spülung + 3-7 0 mol/l + 3-8 0,001 mol/l 0 3-9 0,01 mol/l 0 The oxide degradation is again evaluated as in the examples under point 1). Table 3 Examples Salt concentration Oxide degradation 3-1 0.02 mol / l - 3-2 0.04 mol / l - 3-3 0.10 mol / 1 - 3-4 0.20 mol / l - 3-5 0.40 mol / l - Comparative examples 3-6 without rinsing + 3-7 0 mol / l + 3-8 0.001 mol / l 0 3-9 0.01 mol / l 0

Mit einer Reihe von Einstellungen wird ein Entwicklererschöpfungstest bis zu einer Beladung von 3 m2 Druckplatten/1 l Entwickler durchgeführt. Bei Vergleichsbeispiel 3-7 zeigt sich danach ein starker und bei 3-8 ein leichter Belag auf den Abquetschwalzen, während bei Beispiel 3-3 kein Belag sichtbar ist.With a number of settings, a developer exhaustion test is carried out up to a load of 3 m 2 printing plates / 1 l developer. In Comparative Example 3-7, a thick and then a light coating on the squeeze rollers is shown, while in Example 3-3 no coating is visible.

4. Beispiele von elektrophotographischen Druckformen für die unterschiedlich lange Behandlung der Oxidschicht nach der Hydrophilierung mit der gleichen Salzlösung4. Examples of electrophotographic printing forms for the differently long treatment of the oxide layer after the hydrophilization with the same salt solution

Ein wie in den Beispielen unter Punkt 1) bearbeiteter Flachdruckplattenträger wird nach der Hydrophilierung verschieden lang (Tabelle 4) in 0,02 bis 0,4 molare Sr-Salzlösung getaucht und dann mit einer Lösung beschichtet, die folgende Bestandteile enthält:

  • a) einen organischen Photoleiter,
  • b) ein polymeres, alkalilösliches Bindemittel,
  • c) einen Farbstoff und
  • d) ein Lösemittel oder Lösemittelgemisch mit einem Siedepunkt kleiner 100 °C.
A planographic printing plate support processed as in the examples under point 1) is immersed for different lengths after the hydrophilization (Table 4) in 0.02 to 0.4 molar Sr salt solution and then coated with a solution which contains the following constituents:
  • a) an organic photoconductor,
  • b) a polymeric, alkali-soluble binder,
  • c) a dye and
  • d) a solvent or solvent mixture with a boiling point less than 100 ° C.

In einem speziellen Ausführungsbeispiel enthält die Beschichtungslösung folgende Bestandteile:

5,00 Gew.-%
2,5-Bis(4'-diethylaminophenyl)-1,3,4-oxadiazol,
5,00 Gew.-%
Kresol-Formaldehyd-Novolakharz (entsprechend den Beispielen 1),
0,01 Gew.-%
Rhodamin FB (C.I. 45170) und
ad 100 Gew.-%
Ethylenglykolmonomethylether.
In a special embodiment, the coating solution contains the following components:
5.00% by weight
2,5-bis (4'-diethylaminophenyl) -1,3,4-oxadiazole,
5.00% by weight
Cresol-formaldehyde novolak resin (corresponding to Examples 1),
0.01% by weight
Rhodamine FB (CI 45170) and
ad 100% by weight
Ethylene glycol monomethyl ether.

Die Schichten werden zwei Minuten lang bei 125 °C getrocknet und haben ein Schichtgewicht von 5 g/m2.The layers are dried at 125 ° C. for two minutes and have a layer weight of 5 g / m 2 .

Die so gefertigten, nach dem elektrophotographischen Prinzip arbeitenden Flachdruckplatten werden im Dunkeln mit einer Corona auf -500 V aufgeladen, in Projektion mit 8 Halogenlampen mit je 500 Watt 30 s lang belichtet. Das entstandene latente Ladungsbild wird mit Hilfe einer Magnetwalze mit einem handelsüblichen Toner/Carrier-Gemisch betonert. Nach Wärmefixierung des Toners werden die Nichtbildstellen mit folgender Lösung entfernt: Na2SiO3 2,0 Gew.-% NaOH 0,2 Gew.-% Ethylenglykol 15,0 Gew.-% n-Propanol 10,0 Gew.-% The planographic printing plates produced in this way, which work according to the electrophotographic principle, are charged in the dark with a corona to -500 V, exposed in projection with 8 halogen lamps with 500 watts each for 30 s. The resulting latent charge image is reinforced with a commercially available toner / carrier mixture using a magnetic roller. After heat-fixing the toner, the non-image areas are removed with the following solution: Na 2 SiO 3 2.0% by weight NaOH 0.2% by weight Ethylene glycol 15.0% by weight n-propanol 10.0% by weight

Untersucht wird, inwieweit es beim 5 Minuten erfordernden Entschichtungsvorgang zu einem Angriff auf die Oxidschicht des Trägers kommt. Tabelle 4 Tauchzeit in Sekunden Oxidabbau 0 + 1 - 2 - 5 - 10 - 60 - It is examined to what extent there is an attack on the oxide layer of the support in the 5 minute stripping process. Table 4 Dive time in seconds Oxide degradation 0 + 1 - 2nd - 5 - 10th - 60 -

Wie der Tabelle 4 zu entnehmen ist, kommt es nur beim Unterlassen einer Behandlung mit der Salzlösung zu einem erheblichen oxidabbau, während schon ein sehr kurzes Eintauchen in die Salzlösung (1 s) den Oxidabbau unterbindet.As can be seen in Table 4, only if treatment with the salt solution is omitted does a significant oxide breakdown occur, while a very brief immersion in the salt solution (1 s) prevents the oxide breakdown.

Claims (19)

  1. Process for the treatment of grained and anodized litho printing plates for reducing the decomposition of the metal oxide layer which forms during the anodizing, comprising the successive steps of making the litho printing plate hydrophilic with polyvinylphosphonic acid and treating the litho printing plate made hydrophilic with a salt solution of divalent or polyvalent cations which has a concentration of at least 0.02 mol/l, in which the salt solution contains a salt from the group MgCl2, Mg(NO3)2, CaCl2, Ca(N)3)2, calcium acetate, SrCl2, strontium laevulinate, BaCl2, Ba(NO3)2, ScCl3, Sc2(SO4)3, LaCl3, La(NO3)3, TiCl3, VSO4, CrCl2, MnBr2, NiCl2, CuCl2, ZnSO4, AlCl3, SnCl2 or lead acetate.
  2. Process according to claim 1, characterised by the process steps of coating the litho printing plate with a photo-sensitive layer, exposing this layer and developing the exposed layer with an aqueous-alkaline solution.
  3. Process according to claim 2, characterised in that the application of the salt solution takes place by spraying, dipping or washing after the making of the front side hydrophilic and prior to the application of the photo-sensitive coating to the litho printing plate.
  4. Process according to claim 3, characterised in that the rear side of the litho printing plate is washed with the salt solution simultaneously with the front side.
  5. Process according to claim 2, characterised in that the washing of the rear side of the litho printing plate with the salt solution takes place after the making hydrophilic and after the application of the photo-sensitive coating.
  6. Process according to claim 1, characterised in that the concentration of the salt solution lies in the range from 0.04 to 0.4 mol/l.
  7. Process according to claim 1, characterised in that the temperature of the salt solution comes to 20 to 90 °C.
  8. Process according to claim 1, characterised in that the exposure time of the salt solution is between one second and one minute.
  9. Process according to claim 1, characterised in that the cation of the salt solution is an ion of an element of the 2nd or 3rd main group or of the 3rd sub-group of the periodic system.
  10. Process according to claim 1, characterised in that the cation is calcium.
  11. Process according to claim 1, characterised in that the cation of the salt solution is an ion of an element from the group V, Cr, Mn, Fe, Co, Ni, Zn, Sn and Pb.
  12. Process according to claim 2, characterised in that the aqueous-alkaline solution contains silicate.
  13. Process according to claim 1, characterised in that the litho printing plate is prior to the application of a photo-sensitive coating dipped for between 1 and 60 s in a more than 0.02 mol calcium salt solution at a temperature in the range from 20 to 90 °C.
  14. Process according to claim 2, characterised in that the rear side of the litho printing plate is after the application of a photo-sensitive coats sprayed for between 1 and 60 s at 20 to 90 °C with a calcium salt solution in the concentration range from 0.02 to 0.40 mol/l.
  15. Process according to claim 1, characterised in that a litho printing plate is after the making hydrophilic and prior to the application of a photo-sensitive coating dipped for 1 to 60 s in a 0.02 to 0.4 mol strontium salt solution.
  16. Litho printing plate manufactured by the method according to claims 1 and 2, characterised in that the aluminium support of the litho printing plate is coated with a copying varnish film with a film weight of 1 to 3 g/m2 and that the copying varnish film is formed by drying of a copying varnish solution which contains the following components:
    a) a cresol-formaldehyde-novolak resin,
    b) an esterification product of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonyl chloride with a phenol derivative,
    c) a compound forming a strong acid on irradiation,
    d) a cationic pigment and
    e) a solvent or solvent mixture with a boiling point of less than 200 °C.
  17. Litho printing plate manufactured by the method according to claims 1 and 2, characterised in that the aluminium support of the litho printing plate is coated with a copying varnish film with a film weight of 1 to 3 g/m2 and that the copying varnish film is formed by drying of a copying varnish solution which contains the following components:
    a) a cresol-formaldehyde-novolak resin,
    b) an esterification product of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonyl chloride with a phenol derivative,
    c) a compound forming a strong acid on irradiation,
    d) a cationic pigment and
    e) a silica filler with a mean particle size of 3 to 5 µm,
    f) a surfactant based on dimethyl siloxane and ethylene oxide units and
    g) a solvent or solvent mixture with a boiling point of less than 200 °C.
  18. Litho printing plate manufactured by the method according to claims 1 and 2, characterised in that the aluminium support of the litho printing plate is coated with a copying varnish film whose film weight comes to 1 to 5 g/m2 and that the copying varnish film is formed by drying of a copying varnish solution which contains the following components:
    a) a compound with at least one olefinically unsaturated double bond,
    b) a polymeric, alkali-soluble binder with an acid number of more than 10,
    c) a photoinitiator,
    d) a pigment and
    e) a solvent or solvent mixture with a boiling point of less than 200 °C.
  19. Litho printing plate manufactured by the method according to claims 1 and 2, characterised in that the aluminium support of the litho printing plate is coated with a photo-sensitive electrophotographic layer whose layer weight comes to 3 to 8 g/m2 and that this layer is formed by drying of a coating solution which contains the following components:
    a) an organic photo-conductor,
    b) a polymeric, alkali-soluble binder,
    c) a pigment and
    d) a solvent or solvent mixture with a boiling point of less than 100 °C.
EP92117258A 1991-10-16 1992-10-09 Method for treatment of grained and anodised lithographic printing plates and lithographic printing plates produced according to this method Expired - Lifetime EP0537633B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4134143 1991-10-16
DE4134143A DE4134143A1 (en) 1991-10-16 1991-10-16 METHOD FOR MANUFACTURING FLAT PRESSURE FORMS AND FLAT PRINTING MAKES PRODUCED THEREOF

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EP0537633A1 EP0537633A1 (en) 1993-04-21
EP0537633B1 true EP0537633B1 (en) 1996-12-11

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US (1) US5314787A (en)
EP (1) EP0537633B1 (en)
JP (1) JPH05221178A (en)
DE (2) DE4134143A1 (en)

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3126636A1 (en) * 1981-07-06 1983-01-27 Hoechst Ag, 6000 Frankfurt HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE
DE3406101A1 (en) * 1984-02-21 1985-08-22 Hoechst Ag, 6230 Frankfurt METHOD FOR THE TWO-STAGE HYDROPHILIZING TREATMENT OF ALUMINUM OXIDE LAYERS WITH AQUEOUS SOLUTIONS AND THE USE THEREOF IN THE PRODUCTION OF OFFSET PRINT PLATE CARRIERS
DE3667260D1 (en) * 1985-10-10 1990-01-11 Eastman Kodak Co TREATED ANODIZED ALUMINUM CARRIER AND LITHOGRAPHIC PRINTING PLATE CONTAINING THE TAEGER.
US4983497A (en) * 1985-10-10 1991-01-08 Eastman Kodak Company Treated anodized aluminum support and lithographic printing plate containing same

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DE59207665D1 (en) 1997-01-23
US5314787A (en) 1994-05-24
JPH05221178A (en) 1993-08-31
EP0537633A1 (en) 1993-04-21
DE4134143A1 (en) 1993-06-24

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