EP0537633A1 - 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 PDFInfo
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- EP0537633A1 EP0537633A1 EP92117258A EP92117258A EP0537633A1 EP 0537633 A1 EP0537633 A1 EP 0537633A1 EP 92117258 A EP92117258 A EP 92117258A EP 92117258 A EP92117258 A EP 92117258A EP 0537633 A1 EP0537633 A1 EP 0537633A1
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- planographic printing
- printing plate
- salt solution
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- radiation
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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 process for the production of planographic printing plates from roughened, anodized and hydrophilized planographic printing plates, which are coated, exposed to radiation and developed in an aqueous alkaline solution, and planographic printing plates produced thereafter.
- Aluminum substrates in the form of strips, plates or foils, which are provided with positive or negative working radiation-sensitive coatings, are used as presensitized planographic printing plates.
- 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, -SO3H, -PO3H2, -SH, -OH and -NH2.
- the developer solutions generally contain alkali silicates as alkaline components.
- Silicates have the advantage that they attack the Al2O3 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 carrier and the consequent contamination of the printing forms and of the development devices are avoided or effectively reduced.
- planographic printing plate is treated with a salt solution of a divalent or polyvalent cation in a concentration of at least 0.02 mol / l after the hydrophilization.
- 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 1 second and 1 minute.
- the application of the salt solution is carried out using the usual techniques, eg. B. spraying, rinsing or dipping, easiest after hydrophilizing the front and before applying the light-sensitive coating.
- the back 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 distinguished 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 forms according to the invention results from claims 18 to 20.
- 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 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 of the 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 of 1,2-naphthoquinone -2-dazid-4-sulfonyl chloride, 0.05% by weight victoria pure blue (CI 44045) and ad 100 wt .-% of a solvent mixture of methyl ethyl ketone and propylene glycol monomethyl ether (40/60).
- Mw molecular weight
- the copy varnish film is dried at 125 ° C for one minute.
- the film weight is 1 to 3 g / m2, in particular 2.4 g / m2.
- 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 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 of the 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 of 2- (4-styrylphenyl) -4,6-bis-trichloromethyl-s-triazine, 0.10% by weight crystal violet (CI 42555) and 1.00% by weight of silica filler with an average grain size of 3.9 ⁇ m, 0.10% by weight of surfactant based on dimethylsiloxane and ethylene oxide units, ad 100 wt .-% of a solvent mixture of te
- the copy lacquer film is dried at 125 ° C. for 1 minute.
- the film weight is 1.8 g / m2.
- 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 copying behavior i.e. light sensitivity, reproduction, color fog, susceptibility to under-radiation
- the printing behavior ie free running, water requirement, support
- 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 of dibenzalacetone, 0.05% by weight of 9-phenylacridine, 0.10% by weight of an azo dye composed of 2,4-dinitro6-chlorobenzenediazonium chloride and 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethyl-aniline and ad 100 wt .-% ethylene glycol monomethyl ether.
- Mw molecular weight
- the copy lacquer film is dried for two minutes at 125 ° C. and has a layer weight of 3.0 g / m2.
- the barrier layer After drying for 1 minute at 125 ° C, the barrier layer has a layer weight of 2.0 g / m2.
- the presensitized planographic printing plates thus obtained are exposed as in the examples in item 1) for 35 s and then in a developing device as in the examples in item 1) with an upstream demineralized water rinse of the front to remove the PVAl cover layer at a processing speed of 0.6 m / min in a potassium silicate developer with a total alkali content of 0.55 mol / l and a non-ionic wetting agent content (coconut fatty alcohol polyoxyethylene ether with approx. 8 oxyethylene units (Genapol C080 from Hoechst AG)) of 1 g / l .
- the oxide degradation is again evaluated as in the examples under point 1).
- a developer exhaustion test is carried out with a number of settings up to a load of 3 m 2 printing plates / 1 l developer.
- Comparative Example 3-7 a thick and then 3-8 light coating on the squeeze rollers is shown, while in Example 3-3 no coating is visible.
- the coating solution contains the following components: 5.00% by weight of 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 of rhodamine FB (CI 45170) and ad 100 wt .-% ethylene glycol monomethyl ether.
- the layers are dried at 125 ° C. for two minutes and have a layer weight of 5 g / m2.
- planographic printing plates made 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 emphasized with the aid of a magnetic roller with a commercially available toner / carrier mixture.
- the non-image areas are removed with the following solution: Na2SiO3 2.0% by weight NaOH 0.2% by weight Ethylene glycol 15.0% by weight n-propanol 10.0% by weight
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Abstract
Description
Die Erfindung betrifft ein verfahren zur Herstellung von Flachdruckformen aus aufgerauhten, eloxierten und hydrophilierten Flachdruckplatten, die strahlungsempfindlich beschichtet, belichtet und in einer wäßrig-alkalischen Lösung entwickelt werden, und danach hergestellte Flachdruckformen.The invention relates to a process for the production of planographic printing plates from roughened, anodized and hydrophilized planographic printing plates, which are coated, exposed to radiation and developed in an aqueous alkaline solution, and planographic printing plates produced thereafter.
Als vorsensibilisierte Flachdruckplatten werden Aluminiumträger in Band-, Platten- oder Folienform verwendet, die mit positiv oder negativ arbeitenden strahlungsempfindlichen Beschichtungen versehen sind.Aluminum substrates in the form of strips, plates or foils, which are provided with positive or negative working radiation-sensitive coatings, are used as presensitized planographic printing plates.
Folgende strahlungsempfindlichen Beschichtungen werden üblicherweise hierfür eingesetzt:
- positiv oder negativ arbeitende Diazoverbindungen,
- negativ arbeitende Mischungen aus olefinisch ungesättigten Verbindungen und Photoinitiatoren und
- positiv arbeitende Mischungen mit Photohalbleitern.
- 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 gegenbenenfalls 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, -SO₃H, -PO₃H₂, -SH, -OH and -NH₂.
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 Al₂O₃ 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 Al₂O₃ formed on the front and back of the aluminum support is subject to a strong degradation in the development process. This creates a gel-like coating, in particular on the back of the aluminum carrier, which has only a relatively thin oxide coating, which accumulates on the squeeze rollers of the developing devices and from there can be transferred back to the developed planographic printing plates. In order to avoid the resulting disturbances 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 carrier and the consequent contamination of the printing forms and of the development devices are avoided or effectively reduced.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Flachdruckplatte nach der Hydrophilierung mit einer Salzlösung eines zwei- oder mehrwertigen Kations in einer Konzentration von mindestens 0,02 mol/l behandelt wird.This object is achieved in that the planographic printing plate is treated with a salt solution of a divalent or polyvalent cation in a concentration of at least 0.02 mol / l after the hydrophilization.
Kationkonzentrationen 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 1 Sekunde und 1 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 1 second and 1 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 Rückseite 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 application of the salt solution is carried out using the usual techniques, eg. B. spraying, rinsing or dipping, easiest after hydrophilizing the front and before applying the light-sensitive coating. The back 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 10 bis 16.The further design of the method results from the procedural measures of claims 10 to 16.
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 Flachdruckformen zeichnen sich dadurch aus, daß der Aluminiumträger der Flachdruckplatte mit einem Kopierlackfilm beschichtet ist und daß der Kopierlackfilm durch Trocknen einer Kopierlacklösung gebildet wird. Die Ausgestaltung weiterer Flachdruckformen nach der Erfindung ergibt sich aus den Ansprüchen 18 bis 20.The planographic printing plates produced by the process according to the invention are distinguished 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 forms according to the invention results from claims 18 to 20.
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 Vergleichsbeispielen gegenübergestellt.The following examples explain the subject matter of the invention in detail and are compared with the comparative examples.
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) 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 of the 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 of 1,2-naphthoquinone -2-dazid-4-sulfonyl chloride,
0.05% by weight victoria pure blue (CI 44045) and
ad 100 wt .-% of 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 / m², in particular 2.4 g / m².
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:
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-Novolaknarz,
- 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.
- a) a cresol-formaldehyde novolac 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 of the 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 of 2- (4-styrylphenyl) -4,6-bis-trichloromethyl-s-triazine,
0.10% by weight crystal violet (CI 42555) and
1.00% by weight of silica filler with an average grain size of 3.9 µm,
0.10% by weight of surfactant based on dimethylsiloxane and ethylene oxide units,
ad 100 wt .-% of 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 / m².
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.
- 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.
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) 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-Dinitro6-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 of dibenzalacetone,
0.05% by weight of 9-phenylacridine,
0.10% by weight of an azo dye composed of 2,4-dinitro6-chlorobenzenediazonium chloride and 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethyl-aniline and
ad 100 wt .-% 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 / m².
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 (NO₃) 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 of polyvinyl alcohol with a residual acetyl group content of 10.7%, the 4% strength 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 wt .-% deionized 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 / m².
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 in item 1) for 35 s and then in a developing device as in the examples in item 1) with an upstream demineralized water rinse of the front to remove the PVAl cover layer at a processing speed of 0.6 m / min in a potassium silicate developer with a total alkali content of 0.55 mol / l and a non-ionic wetting agent content (coconut fatty alcohol polyoxyethylene ether with approx. 8 oxyethylene units (Genapol C080 from Hoechst AG)) of 1 g / l .
Der Oxidabbau wird wiederum wie in den Beispielen unter Punkt 1) bewertet.
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 Ahquetschwalzen, während bei Beispiel 3-3 kein Belag sichtbar ist.A developer exhaustion test is carried out with a number of settings up to a load of 3 m 2 printing plates / 1 l developer. In Comparative Example 3-7, a thick and then 3-8 light coating on the squeeze rollers is shown, while in Example 3-3 no coating is visible.
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) 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 of 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 of rhodamine FB (CI 45170) and
ad 100 wt .-% 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 / m².
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:
Untersucht wird, inwieweit es beim 5 Minuten erfordernden Entschichtungsvorgang zu einem Angriff auf die Oxidschicht des Trägers kommt.
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 (20)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4134143A DE4134143A1 (en) | 1991-10-16 | 1991-10-16 | METHOD FOR MANUFACTURING FLAT PRESSURE FORMS AND FLAT PRINTING MAKES PRODUCED THEREOF |
DE4134143 | 1991-10-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0537633A1 true EP0537633A1 (en) | 1993-04-21 |
EP0537633B1 EP0537633B1 (en) | 1996-12-11 |
Family
ID=6442739
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92117258A Expired - Lifetime EP0537633B1 (en) | 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 |
Country Status (4)
Country | Link |
---|---|
US (1) | US5314787A (en) |
EP (1) | EP0537633B1 (en) |
JP (1) | JPH05221178A (en) |
DE (2) | DE4134143A1 (en) |
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-
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- 1992-10-09 DE DE59207665T patent/DE59207665D1/en not_active Expired - Fee Related
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Also Published As
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DE59207665D1 (en) | 1997-01-23 |
JPH05221178A (en) | 1993-08-31 |
EP0537633B1 (en) | 1996-12-11 |
DE4134143A1 (en) | 1993-06-24 |
US5314787A (en) | 1994-05-24 |
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