EP0925916B1 - Rückstandsfreies Aufzeichnungselement ohne Materialabtrag für die Herstellung von Flachdruckplatten mit unterschiedlicher Farbdichte zwischen Bild und Nicht-Bild - Google Patents

Rückstandsfreies Aufzeichnungselement ohne Materialabtrag für die Herstellung von Flachdruckplatten mit unterschiedlicher Farbdichte zwischen Bild und Nicht-Bild Download PDF

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Publication number
EP0925916B1
EP0925916B1 EP19980203792 EP98203792A EP0925916B1 EP 0925916 B1 EP0925916 B1 EP 0925916B1 EP 19980203792 EP19980203792 EP 19980203792 EP 98203792 A EP98203792 A EP 98203792A EP 0925916 B1 EP0925916 B1 EP 0925916B1
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Prior art keywords
image
layer
imaging element
hydrophilic
printing plate
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EP19980203792
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English (en)
French (fr)
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EP0925916A1 (de
Inventor
Luc Leenders
Ludo Van Rompuy
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern

Definitions

  • the present invention relates to method of making a lithographic printing plate. More specifically the invention is related to a method of making a lithographic printing plate comprising the exposure of a heat sensitive imaging element comprising as top layer an image-recording layer containing an IR-cyanine dye.
  • Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink.
  • the areas which accept ink define the printing image areas and the ink-rejecting areas define the background areas.
  • a photographic material is made imagewise receptive to oily or greasy inks in the photo-exposed (negative-working) or in the non-exposed areas (positive-working) on a hydrophilic background.
  • lithographic printing plates also called surface litho plates or planographic printing plates
  • a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition.
  • Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
  • the exposed image areas become insoluble and the unexposed areas remain soluble.
  • the plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
  • printing plates are known that include a photosensitive coating that upon image-wise exposure is rendered soluble at the exposed areas. Subsequent development then removes the exposed areas.
  • a typical example of such photosensitive coating is a quinone-diazide based coating.
  • the above described photographic materials from which the printing plates are made are exposed in contact through a photographic film that contains the image that is to be reproduced in a lithographic printing process.
  • Such method of working is cumbersome and labor intensive.
  • the printing plates thus obtained are of superior lithographic quality.
  • GB- 1 492 070 discloses a method wherein a metal layer or a layer containing carbon black is provided on a photosensitive coating. This metal layer is then ablated by means of a laser so that an image mask on the photosensitive layer is obtained. The photosensitive layer is then overall exposed by UV-light through the image mask. After removal of the image mask, the photosensitive layer is developed to obtain a printing plate.
  • This method however still has the disadvantage that the image mask has to be removed prior to development of the photosensitive layer by a cumbersome processing.
  • US-P- 4 708 925 discloses imaging elements including a photosensitive composition comprising an alkali-soluble novolac resin and an onium-salt.
  • This composition can optionally contain an IR-sensitizer. After image-wise exposing said imaging element to UV - visible - or IR-radiation followed by a development step with an aqueous alkali liquid there is obtained a positive or negative working printing plate. A processing step is required and the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 625 728 discloses an imaging element comprising a layer which is sensitive to UV- and IR-irradiation and which can be positive or negative working.
  • This layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance.
  • a processing step is required and the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • US-P- 5 340 699 is almost identical with EP-A- 625 728 but discloses the method for obtaining a negative working IR-laser recording imaging element.
  • the IR-sensitive layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance.
  • a processing step is required and the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 678 380 discloses a method wherein a protective layer is provided on a grained metal support underlying a laser-ablatable surface layer. Upon image-wise exposure the surface layer is fully ablated as well as some parts of the protective layer. The printing plate is then treated with a cleaning solution to remove the residu of the protective layer and thereby exposing the hydrophilic surface layer. Here also a processing step is required.
  • EP-A- 864 420 discloses a heat mode imaging element for making lithographic printing plates comprising on a lithographic base having a hydrophilic surface an intermediate layer comprising a polymer, soluble in an aqueous alkaline solution and a top layer that is sensitive to IR-radiation wherein said top layer upon exposure to IR-radiation has a decreased or increased capacity for being penetrated and/or solubilised by an aqueous alkaline solution. This material does not give a selective dissolution of the exposed or unexposed parts of the top and intermediate layer.
  • DD- 217 645 discloses a method for providing lithographic plates by irradiation with laser with one or more dyes adapted for the wavelenght of the laser, comprising non light-sensitive hydrophilic material on a support and wherein the concentration gradient of the sensitizing dyes lies perpendicular on the surface of the support.
  • EP-A- 652 483 discloses a lithographic plate imageable by IR-light and requiring no dissolution processing.
  • the lithographic printing plate comprises a substrate bearing a heat-sensitive coating comprising a photothermal converter, which coating becomes relatively more hydrophilic under the action of heat.
  • the photothermal converter is perferably an IR-absorbing dye which generates an acid upon irradiation.
  • DD- 217 914 discloses the preparation of a lithographic plate by irradiation with a laser of a non-light sensitive hydrophilic material, coated on an anodic aluminuùm support, which can comprises dyes or other additions, wherein the aluminumoxide layer is coloured with a dye, which absorbs at the wavelenght of the laser.
  • DD- 213 530 discloses a method for the preparation of printing plates for flexographic and lithographic printing by irradiation with a laser of layers comprising spectral sensitizers wherein spectral sensitizers are used whose spectrum changes by irradiation.
  • EP-A- 694 586 discloses indolenine cyanine disulphonic acid derivaztives as IR-absorbing dyes.
  • US-P- 4 034 183 discloses an improvement in the process for the production of a planographic printing form in which a carrier coated with a hydrophilic layer composed of a non-light-sensitive compound is imagewise exposed, the improvement comprising imagewise exposing the layer to laser irradiation of an intensity and for a period such that the exposed areas are rendered hydrophobic and oleophilic.
  • a method of making a lithographic printing plate comprising the steps of:
  • the heat-sensitive imaging element used in the method in accordance with the present invention comprises an IR-cyanine dye.
  • a mixture of IR-cyanine dyes may be used, but it is preferred to use only one IR-cyanine dye.
  • Particularly useful IR-cyanine dyes are cyanines dyes with two acid groups, more preferably with two sulphonic groups. Still more preferably are cyanines dyes with two indolenine and two sulphonic acid groups. Most preferably is compound I with the structure as indicated
  • Said dye is preferably present in said top layer preferably in an amount between 0.01 and 1 g/m 2 , more preferably in an amount between 0.05 and 0.20 g/m 2 .
  • the top layer or the layer just underlying said top layer preferably includes a compound capable of converting light into heat.
  • Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for image-wise exposure.
  • Particularly useful compounds are for example dyes and in particular infrared dyes which can be the same as mentioned above, carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO 2.9 .
  • conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions.
  • Said compound capable of converting light into heat is preferably present in the top layer but can also be included in an underlying layer.
  • Said compound capable of converting light into heat is present in the imaging element preferably in an amount between 0.01 and 1 g/m 2 , more preferably in an amount between 0.05 and 0.50 g/m 2 .
  • the top layer comprises hydrophobic particles dispersed in a cross-linked hydrophilic layer.
  • a particularly suitable cross-linked hydrophilic layer may be obtained from a hydrophilic binder cross-linked with a cross-linking agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolysed tetraalkyl orthosilicate. The latter is particularly preferred; most preferred is tetraethyl or tetramethyl orthosilicate.
  • hydrophilic binder there may be used hydrophilic (co)polymers such as for example, homopolymers and copolymers of acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
  • the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60 percent by weight, preferably 80 percent by weight.
  • a preferred hydrophilic binder is polyvinylalcohol.
  • the amount of crosslinking agent, in particular of tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1.0 parts by weight and 3 parts by weight.
  • a cross-linked hydrophilic layer used in accordance with the present invention preferably also contains substances that increase the mechanical strength and the porosity of the layer.
  • colloidal silica may be used.
  • the colloidal silica employed may be in the form of any commercially available water-dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm.
  • inert particles of larger size than the colloidal silica can be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides.
  • the surface of the cross-linked hydrophilic layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage sites for water in background areas.
  • the thickness of a cross-linked hydrophilic layer in a lithographic base in accordance with this embodiment may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
  • the hydrophobic polymer particles preferred in the embodiment of this invention are thermoplastic polymer particles.
  • the hydrophobic thermoplastic polymer particles used in connection with the present invention preferably have a coagulation temperature above 50°C and more preferably above 70°C. Coagulation may result from softening or melting of the thermoplastic polymer particles under the influence of heat.
  • There is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles however the temperature should be sufficiently below the decomposition temperature of the polymer particles.
  • the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs.
  • hydrophobic polymer particles for use in connection with the present invention having preferably a Tg above 80°C are preferably polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole, copolymers or mixtures thereof. Most preferably used are polystyrene, polymethylmethacrylate or copolymers thereof.
  • the weight average molecular weight of the polymers may range from 5,000 to 1,000,000g/mol as determined by GPC relative to polystyrene standards.
  • the hydrophobic particles may have a particle size from 0.01 ⁇ m to 50 ⁇ m, more preferably between 0.05 mm and 10 mm and most preferably between 0.05 ⁇ m and 2 ⁇ m.
  • the polymer particles are present as a dispersion in the aqueous coating liquid of the image-forming layer and may be prepared by the methods disclosed in US-P- 3 476 937 .
  • Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
  • the amount of hydrophobic thermoplastic polymer particles contained in the image-forming layer is preferably at least 20% by weight and more preferably at least 30% by weight and most preferably at least 40% by weight.
  • the top layer comprises switchable polymers.
  • Switchable polymers are polymers which by heating undergo a transition from hydrophobic to hydrophilic or vice versa.
  • An example of a switchable polymer is poly-tetrahydropyranolmethacrylate.
  • the support of the imaging element can be flexible or rigid.
  • flexible support in connection with the present invention all kinds of flexible support can be used e. g. paper, polyethylene coated paper, but it is particularly preferred to use a plastic film e.g. substrated polyethylene terephthalate film, cellulose acetate film, polystyrene film, polycarbonate film, polyethylene film, polypropylene film.
  • the plastic film support may be opaque or transparent.
  • the amount of silica in the adhesion improving layer is between 200 mg per m2 and 750 mg per m2.
  • the ratio of silica to hydrophilic binder is preferably more than 1 and the surface area of the colloidal silica is preferably at least 300 m2 per gram, more preferably at least 500 m2 per gram.
  • the support can also be rigid, preferably an aluminum foil.
  • a particularly preferred aluminum foil is an electrochemically grained and anodised aluminum support.
  • the anodised aluminum support may be treated to improve the adhesive properties of its surface.
  • the aluminum support may be silicated by treating its surface with sodium silicate solution at elevated temperature, e.g. 95°C.
  • a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
  • the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or can be carried out at a slightly elevated temperature of about 30 to 50°C.
  • a further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution.
  • the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulphonic acid, polyvinylbenzenesulphonic acid, sulphuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulphonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • the imaging element can contain other layers such as subbing layers and antihalo layers.
  • the imaging element optionally contains between the support and the top layer a reflective layer.
  • Said reflective layer can be any layer which reflects the IR-irradiation but is preferably aluminum with a high visual density e.g. vacuum deposited aluminum
  • Imaging in connection with the present invention can be done with a thermal head.
  • an image-wise scanning exposure is used involving the use of a laser that operates in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm.
  • laser diodes emitting in the near-infrared.
  • Exposure of the imaging element can be performed with lasers with a short as well as with lasers with a long pixel dwell time. Preferred are lasers with a pixel dwell time between 0.005 ⁇ s and 20 ⁇ s.
  • the imaging element After the exposure the imaging element is ready to be used as a lithographic printing plate.
  • a dispersion was prepared by mixing 16.8 g of a dispersion containing 21.5% TiO 2 (average particle size 0.3 to 0.5 ⁇ m) and 2.5% polyvinylalcohol in deionized water. Thereto 7.0 respectively 14g of a 20% polystyrene dispersion was added. To these dispersions was added 0.7 respectively 1.4 ml of a hydrolyzed 28.43% tetramethylorthosilicate solution. 0.1 of the IR-dye compound I was added to these dispersions. The dispersions are made up with water to a volume of 40 ml.
  • the imaging elements were kept for 5 days at a temperature of 49°C and relative humidity of 20% in order to harden the polyvinylalcohol.
  • the imaging elements were imaged with
  • a dispersion was prepared by mixing 16.8 g of a dispersion containing 21.5% TiO 2 (average particle size 0.3 to 0.5 ⁇ m) and 2.5% polyvinylalcohol in deionized water. Thereto 11.24 g of a 12.45% polystyrene dispersion was added. To this dispersion was added 0.7 g of a hydrolyzed 28.43% tetramethylorthosilicate solution. 0.1 of a IR-dye compound with the structure as given below was added. The dispersion is made up with water to a volume of 30 ml.
  • This dispersion was well stirred and coated on a subbed PET-support at a thickness of 30 ⁇ m and dried with hot air at 60°C for 2 hours. After coating the imaging element was kept for 5 days at a temperature of 49°C and relative humidity of 20% in order to harden the polyvinylalcohol.
  • the imaging element was imaged with

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Printing Plates And Materials Therefor (AREA)

Claims (8)

  1. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung einer lithografischen Druckplatte :
    Bereitstellen eines wärmeempfindlichen Bilderzeugungselements, das einen Träger und eine Bildaufzeichnungsschicht als Deckschicht enthält, wobei die Bildaufzeichnungsschicht einen IR-absorbierenden Cyaninfarbstoff enthält,
    bildmäßige Belichtung des Bilderzeugungselements mit Infrarotlicht oder Wärme oder Ablatieren der Bildaufzeichnungsschicht, wobei ohne Entwicklungsstufe eine lithografische Druckplatte, die hydrophobe und hydrophile Bereiche in der Schicht enthält, erhalten wird,
    dadurch gekennzeichnet, daß die Belichtung eine Änderung der visuellen optischen Dichte des IR-absorbierenden Cyaninfarbstoffes hervorruft.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der IRabsorbierende Cyaninfarbstoff zwei Säuregruppen enthält.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß der IRabsorbierende Cyaninfarbstoff zwei Indoleningruppen enthält.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der IRabsorbierende Cyaninfarbstoff Verbindung I der nachstehenden Formel I ist :
    Figure 00160001
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Deckschicht hydrophobe, in einer vernetzten hydrophilen Schicht dispergierte Teilchen enthält, wobei die vernetzte hydrophile Schicht aus einem hydrophilen, mit einem Vernetzungsmittel vernetzten Bindemittel erhalten ist.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das hydrophile Bindemittel Polyvinylalkohol ist.
  7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß das Vernetzungsmittel ein hydrolysiertes Tetraalkylorthosilikat ist.
  8. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Deckschicht ein schaltbares Polymer enthält.
EP19980203792 1997-12-09 1998-11-10 Rückstandsfreies Aufzeichnungselement ohne Materialabtrag für die Herstellung von Flachdruckplatten mit unterschiedlicher Farbdichte zwischen Bild und Nicht-Bild Expired - Lifetime EP0925916B1 (de)

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EP97203855 1997-12-09
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EP19980203792 EP0925916B1 (de) 1997-12-09 1998-11-10 Rückstandsfreies Aufzeichnungselement ohne Materialabtrag für die Herstellung von Flachdruckplatten mit unterschiedlicher Farbdichte zwischen Bild und Nicht-Bild

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US11845259B2 (en) 2018-05-14 2023-12-19 Agfa Offset Bv Lithographic printing plate precursor

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DE60033468T2 (de) 1999-06-04 2007-10-31 Fujifilm Corp. Vorläufer für eine lithographische Druckplatte sowie Verfahren zu seiner Herstellung
US6686125B2 (en) 2000-01-14 2004-02-03 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
ATE307846T1 (de) 2000-12-28 2005-11-15 Fuji Photo Film Co Ltd Verfahren zur herstellung feiner polymerpartikel und diese enthaltende lithographische druckplatte
JP2004188848A (ja) 2002-12-12 2004-07-08 Konica Minolta Holdings Inc 印刷版材料
US7323288B2 (en) 2003-04-14 2008-01-29 Kodak Graphic Communications Canada Company Layers in printing plates, printing plates and method of use of printing plates
JP2005096169A (ja) * 2003-09-24 2005-04-14 Konica Minolta Medical & Graphic Inc 平版印刷版材料と印刷方法
EP1614541A3 (de) 2004-07-08 2006-06-07 Agfa-Gevaert Verfahren zur Herstellung einer lithographischen Druckplatte
DE602005005804T2 (de) 2005-06-21 2009-04-09 Agfa Graphics N.V. Wärmeempfindliches Bildaufzeichnungselement
EP3431290B1 (de) 2017-07-20 2021-09-08 Agfa Nv Lithografiedruckplattenvorläufer
EP3587112B1 (de) 2018-06-21 2024-04-03 Eco3 Bv Lithographiedruckplattenvorläufer
EP3587113B1 (de) 2018-06-21 2023-01-04 Agfa Offset Bv Lithographiedruckplattenvorläufer
EP3686011A1 (de) 2019-01-23 2020-07-29 Agfa Nv Lithographiedruckplattenvorläufer
EP3875271A1 (de) 2020-03-04 2021-09-08 Agfa Nv Lithographiedruckplattenvorläufer
EP3892469B1 (de) 2020-04-10 2023-11-08 Eco3 Bv Lithographiedruckplattenvorläufer
US20230266667A1 (en) 2020-06-24 2023-08-24 Agfa Offset Bv A Lithographic Printing Plate Precursor
EP4223534A1 (de) 2022-02-07 2023-08-09 Agfa Offset Bv Lithografiedruckplattenvorläufer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11845259B2 (en) 2018-05-14 2023-12-19 Agfa Offset Bv Lithographic printing plate precursor

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