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EP1065051B1 - Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques - Google Patents

Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques Download PDF

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Publication number
EP1065051B1
EP1065051B1 EP19990202110 EP99202110A EP1065051B1 EP 1065051 B1 EP1065051 B1 EP 1065051B1 EP 19990202110 EP19990202110 EP 19990202110 EP 99202110 A EP99202110 A EP 99202110A EP 1065051 B1 EP1065051 B1 EP 1065051B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive material
material according
layer
hydrophilic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19990202110
Other languages
German (de)
English (en)
Other versions
EP1065051A1 (fr
Inventor
Marc C/O Agfa-Gevaert N.V. Van Damme
Joan C/O Agfa-Gevaert N.V. Vermeersch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP19990202110 priority Critical patent/EP1065051B1/fr
Priority to DE69911933T priority patent/DE69911933T2/de
Priority to US09/599,966 priority patent/US6399276B1/en
Priority to JP2000194256A priority patent/JP2001047758A/ja
Publication of EP1065051A1 publication Critical patent/EP1065051A1/fr
Application granted granted Critical
Publication of EP1065051B1 publication Critical patent/EP1065051B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1033—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials by laser or spark ablation
    • 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
    • B41M5/368—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 involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development

Definitions

  • the present invention relates to a heat mode recording material for making a lithographic plate for use in lithographic printing.
  • the present invention further relates to a method for imaging said heat mode recording material e.g. by means of a laser.
  • Lithographic printing is the process of printing from specially prepared surfaces, some areas of which are capable of accepting ink (oleophilic areas) whereas other areas will not accept ink (hydrophilic areas).
  • oleophilic areas areas of which are capable of accepting ink
  • hydrophilic areas areas of which are capable of accepting ink
  • hydrophilic areas are applied to the plate surface that contains hydrophilic and oleophilic areas.
  • the hydrophilic areas will be soaked with water or the dampening liquid and are thereby rendered oleophobic while the oleophilic areas will accept the ink.
  • DE-A- 2 448 325 discloses a laser heat mode "direct negative" printing plate comprising e.g. a polyester film support provided with a hydrophilic surface layer.
  • the disclosed heat mode recording material is imaged using an Argon laser thereby rendering the exposed areas oleophilic.
  • An offset printing plate is thus obtained which can be used on an printing press without further processing.
  • the plate is called a "direct negative” plate because the areas of the recording material that have been exposed are rendered ink accepting.
  • DE-A- 2 448 325 concern "direct negative" printing plates comprising e.g. hydrophilic aluminium support coated with a water soluble laser light (Argon-488nm) absorbing dye or with a coating based on a mixture of hydrophilic polymer and laser light absorbing dye (Argon - 488nm).
  • heat mode recording materials for preparing "direct negative” printing plates include e.g. US-A- 4 341 183, DE-A- 2 607 207, DD-A- 213 530, DD-A- 217 645 and DD-A- 217 914 . These documents disclose heat mode recording materials that have on an anodized aluminium support a hydrophilic layer.
  • the disclosed heat mode recording materials are image-wise exposed using a laser.
  • Laser exposure renders the exposed areas insoluble and ink receptive, whereas the non exposed image portions remain hydrophilic and water soluble allowing to be removed by the dampening liquid during printing exposing the hydrophilic support.
  • Such plates can be used directly on the press without processing.
  • DD-A- 155 407 discloses a laser heat mode "direct negative" printing plate where a hydrophilic aluminum oxide layer is rendered oleophilic by direct laser heat mode imaging. These printing plates may also be used on the press without further processing.
  • EP-A- 580 393 discloses a lithographic printing plate directly imageable by laser discharge, the plate comprising a topmost first layer and a second layer underlying the first layer wherein the first layer is characterized by efficient absorption of infrared radiation and the first and second layer exhibit different affinities for at least one printing liquid.
  • EP-A- 683 728 discloses a heat mode recording material comprising on a support having an ink receptive surface or being coated with an ink receptive layer a substance capable of converting light into heat and a hardened hydrophilic surface layer having a thickness not more than 3 ⁇ m. The lithographic properties of said material are not very good.
  • a heat-sensitive material for making lithographic plates comprising in the order given on a support an IR-sensitive oleophilic layer and a cross-linked hydrophilic layer, characterized in that said heat-sensitive material is covered with a layer comprising at least an organic compound comprising cationic groups.
  • the organic compounds having cationic groups for use in connection with the present invention are preferably hydrophilic and may be low molecular weight compounds but are preferably polymers.
  • Preferred compounds are those having one or more ammonium groups or amino groups that can be converted to ammonium groups in an acidic medium.
  • An especially preferred type of cationic compounds are polysacharides modified with one or more groups containing an ammonium or amino group.
  • Most preferred organic compounds having cationic groups are dextrans or pullulan wherein at least some of the hydroxy groups have been modified into one or more of the following groups: -O-R 1 -O-CO-R 2 wherein R 1 represents an organic residue containing an amino or ammonium group, e.g. an amine substituted alkyl, an amine substituted alkylaryl etc..
  • R 2 has one of the significances given for R 1 or stands for -OR 3 or -N(R 4 )R 5 , wherein R 3 has one of the significances given for R 1 and each of R 4 and R 5 which may be the same or different and have one of the significances given for R 1 .
  • Pullulan is a polysacharide that is produced by microorganisms of the Aureobasidium pullulans type (Pullularia pullulans) and that contains maltotriose repeating units connected by a a-1,6 glycosidic bond. Pullulan is generally produced on industrial scale by fermentation of partially hydrolysed starch or by bacterial fermentation of sucrose. Pullulan is commmercially available from e.g. Shodex, Pharmacosmos.
  • dextrans or pullulan suitable for use in accordance with the present invention are dextrans or pullulan wherein some of the hydroxyl groups have been modified in one of the groups shown in table 1.
  • the modified dextrans or pullulan can be prepared by a reaction of a dextran with e.g. alkylating agents, chloroformates, acid halides, carboxylic acids etc...
  • the organic compound having one or more cationic groups according to the invention is preferably provided in an amount of 10 to 2000 mg/m 2 and more preferably in an amount of 20 to 1000 mg/m 2 .
  • hydrophilic coatings are preferably cast from aqueous compositions containing hydrophilic binders having free reactive groups including e.g. hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl, etc., along with suitable crosslinking or modifying agents including e.g. hydrophilic organotitanium reagents, aluminoformyl acetate, dimethylol urea, melamines, aldehydes, hydrolyzed tetraalkyl orthosilicate, etc..
  • hydrophilic organotitanium reagents e.g. hydrophilic organotitanium reagents, aluminoformyl acetate, dimethylol urea, melamines, aldehydes, hydrolyzed tetraalkyl orthosilicate, etc.
  • Suitable polymers for hydrophilic layers may be selected from the group consisting of gum arabic, casein, gelatin, starch derivatives, carboxymethyl cellulose and Na salt thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, hydroxyethylene polymers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinylacetate having a hydrolyzation degree of at least 60% by weight and more preferably at least 80% by weight.
  • Hydrophilic layers containing polyvinylalcohol or polyvinylacetate hydrolyzed to an extent of at least 60% by weight hardened with a tetraalkyl orthosilicate, e.g. tetraethyl orthosilicate or tetramethyl orthosilicate, as disclosed in e.g. US-P- 3 476 937 are particularly preferred because their use in the present heat mode recording material results in excellent lithographic printing properties.
  • a further suitable hardened hydrophilic surface layer is disclosed in EP-A- 514 990 .
  • the hydrophilic layer disclosed in this EP-application comprises the hardening reaction product of a (co)polymer containing amine or amide functions having at least one free hydrogen (e.g. amino modified dextrane) and aldehyde.
  • a cross-linked hydrophilic binder in the heat-sensitive layer used in accordance with the present embodiment preferably also contains substances that increase the mechanical strength and the porosity of the layer e.g. metal oxide particles which are particles of titanium dioxide or other metal oxides. Incorporation of these particles gives the surface of the cross-linked hydrophilic layer a uniform rough texture consisting of microscopic hills and valleys.
  • these particles are oxides or hydroxydes of beryllium, magnesium, aluminium, silicon, gadolinium, germanium, arsenic, indium, tin, antimony, tellurium, lead, bismuth or a transition metal.
  • Particularly preferable particles are oxides or hydroxides of aluminum, zirconium, silicon and titanium, used in 20 to 95 % by weight of the hydrophilic layer, more preferably in 30 to 90% by weight of the hydrophilic layer.
  • the cross-linked hydrophilic layer is preferably coated at a dry thickness of 0.3 to 5 ⁇ m, more preferably at a dry thickness of 0.5 to 3 ⁇ m.
  • the hardened hydrophilic layer may comprise additional substances such as e.g. plasticizers, pigments, dyes etc.
  • the cross-linked hydrophilic layer can additionally contain an IR-absorbing compound in order to increase the IR-sensitivity.
  • the IR-sensitive oleophilic layer comprises an oleophilic binder and a compound capable of converting light into heat.
  • Suitable compounds capable of converting light into heat are preferably infrared absorbing components having an absorption 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 as disclosed in EP-A- 908 307 and pigments and in particular infrared pigments such as 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.
  • the lithographic performance and in particular the print endurance obtained depends i.a.on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
  • the oleophilic polymer is selected from the group consisting of polyvinyl chloride, polyesters, polyurethanes, novolac, polyvinyl carbazole etc., copolymers or mixtures thereof.
  • the polymeric binder in the recording layer is heat sensitive: e.g. a polymer containing nitrate ester groups (e.g. self oxidizing binder cellulose nitrate as disclosed in GB-P- 1 316 398 and DE-A- 2 512 038 ); e.g. a polymer containing carbonate groups (e.g. polyalkylene carbonate); e.g. a polymer containing covalently bound chlorine (e.g. polyvinylidene chloride). Also substances containing azo or azide groups , capable of liberating N 2 upon heating are favourably used.
  • nitrate ester groups e.g. self oxidizing binder cellulose nitrate as disclosed in GB-P- 1 316 398 and DE-A- 2 512 038
  • carbonate groups e.g. polyalkylene carbonate
  • chlorine e.g. polyvinylidene chloride
  • substances containing azo or azide groups capable of liberating N 2 upon heating
  • the oleophilic layer is coated at a dry weight from 0.5 to 30 g/m 2 , preferably from 3 to 15 g/m 2 .
  • the support according to the present invention is preferably dimensionally stable and can be aluminum or another metal or alloy.
  • Preferentially electrochemically and/or mechanically grained and anodised aluminum is used in the present invention..
  • the support can be a flexible support.
  • flexible support in connection with the present embodiment it is particularly preferred to use a plastic film e.g. substrated polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, polyethylene film, polypropylene film, polyvinyl chloride film, polyether sulphone film.
  • the plastic film support may be opaque or transparent.
  • the plastic film is preferably subbed with subbing layers as described in EP-A- 619 524 , EP-A- 619 525 and EP-A- 620 502 .
  • Still further paper or glass of a thickness of not more than 1.2 mm can also be used.
  • the imaging element is image-wise exposed.
  • the cover layer and the cross-linked hydrophilic layer can be removed and said areas are converted to oleophilic areas while the unexposed areas remain hydrophilic.
  • This is mostly the case when using short pixel dwell times (for example 1 to 100 ns).
  • longer pixel dwell times for example 1 to 20 ⁇ s
  • the hydrophilic layer is not or only partially removed.
  • the remaining parts of the hydrophilic layer can be removed on the press by contact with fountain solution and ink or by an additional wet or dry processing step between the IR-laser exposure and the start-up of the printing process.
  • Image-wise exposure in connection with the present invention is preferably an image-wise scanning exposure involving the use of a laser or L.E.D.
  • a laser or L.E.D Preferably used are lasers that operate in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are laser diodes emitting in the near-infrared with an intensity greater than 0.1 mW/ ⁇ m 2 .
  • the plate is then ready for printing without an additional development and can be mounted on the printing press.
  • the imaging element is first mounted on the printing cylinder of the printing press and then image-wise exposed directly on the press. Subsequent to exposure, the imaging element is ready for printing.
  • the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
  • the printing plate is soldered in a cylindrical form by means of a laser.
  • This cylindrical printing plate which has as diameter the diameter of the print cylinder is slid on the print cylinder instead of mounting a conventional printing plate. More details on sleeves are given in "Grafisch Nieuws" , 15, 1995, page 4 to 6.
  • the hydrophilic layer was coated to a wet coating thickness of 20 ⁇ m from a solution having the following composition 70.0g TiO 2 - dispersion in water, stabilized with Polyviol WX 48 TM (polyvinyl alcohol from Wacker) (10 % w/w polyvinyl alcohol versus TiO 2 ) ( average particle size 0.3 to 0.5 ⁇ m)-6.25% w/w 30.0g hydrolyzed tetramethyl orthosilicate in water/ethanol-6 .25% w/w 1.2g wetting agent in water-5%w/w
  • the resulting imaging elements were imaged on a Creo 3244 Trendsetter TM at 2400 dpi operating at a drum speed of 80 rpm and a laser output of 15.5 Watt After imaging the plate was mounted on a GTO 52 press using K+E 800 as ink and rotamatic as fountain solution.
  • the press was started by allowing the print cylinder with the imaging element mounted thereon to rotate.
  • the dampener rollers of the press were first dropped on the imaging element so as to supply dampening liquid to the imaging element and after 10 revolutions of the print cylinder, the ink rollers were dropped to supply ink. After 10 further revolutions paper was feeded.
  • the Dmin and the dot area of the 50% screen at 200 lpi were measured at prints 5, 25 and 50 with a Macbeth RD918-SB.

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

Claims (9)

  1. Matériau thermosensible pour la fabrication du cliché lithographique, comprenant, dans l'ordre donné, sur un support, une couche oléophile sensible au rayonnement infrarouge et une couche hydrophile réticulée, caractérisé en ce que ledit matériau thermosensible est recouvert d'une couche comprenant au moins un composé organique comprenant des groupes cationiques.
  2. Matériau thermosensible selon la revendication 1, dans lequel ledit composé organique est un polymère hydrophile contenant un ou plusieurs groupes ammonium ou un composé organique hydrophile à bas poids moléculaire contenant un ou plusieurs groupes ammonium.
  3. Matériau thermosensible selon la revendication 2, dans lequel ledit polymère hydrophile est un polysaccharide.
  4. Matériau thermosensible selon la revendication 3, dans lequel ledit polysaccharide est le dextran ou le pullulane.
  5. Matériau thermosensible selon l'une quelconque des revendications 1 à 4, dans lequel ledit composé organique est compris dans ledit élément de formation d'image en une quantité entre 0,01 et 2,00 g/m2.
  6. Matériau thermosensible selon l'une quelconque des revendications 1 à 5, dans lequel ladite couche oléophile est coulée pour obtenir un poids à sec de 0,75 à 15 g/m2.
  7. Matériau thermosensible selon l'une quelconque des revendications 1 à 6, dans lequel ladite couche hydrophile réticulée comprend des oxydes ou des hydroxydes du béryllium, du magnésium, de l'aluminium, du silicium, du gadolinium, du germanium, de l'arsenic, de l'indium, de l'étain, de l'antimoine, du tellure, du plomb, du bismuth, du titane ou d'un métal de transition.
  8. Matériau thermosensible selon l'une quelconque des revendications 1 à 7, dans lequel la couche hydrophile possède une épaisseur à sec entre 0,3 et 5 µm.
  9. Procédé pour fabriquer des clichés d'impression lithographique, comprenant les étapes consistant à (i) exposer en forme d'image à un faisceau laser possédant une intensité supérieure à 0,1 mW/µm2, un matériau thermosensible selon l'une quelconque des revendications 1 à 8 ; (ii) avant ou après l'étape (i), monter le cliché sur une presse d'impression ; (iii) mettre ledit cliché en contact avec une solution de mouillage et avec de l'encre.
EP19990202110 1999-06-29 1999-06-29 Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques Expired - Lifetime EP1065051B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19990202110 EP1065051B1 (fr) 1999-06-29 1999-06-29 Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques
DE69911933T DE69911933T2 (de) 1999-06-29 1999-06-29 Verarbeitungsfreie Flachdruckplatte mit einer Deckschicht die kationische Gruppen enthaltende Verbindungen enthält
US09/599,966 US6399276B1 (en) 1999-06-29 2000-06-23 Processless printing plate with cover layer containing compounds with cationic groups
JP2000194256A JP2001047758A (ja) 1999-06-29 2000-06-28 カチオン性基を有する化合物を含有する被覆層を有するプロセスレス印刷版

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19990202110 EP1065051B1 (fr) 1999-06-29 1999-06-29 Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques

Publications (2)

Publication Number Publication Date
EP1065051A1 EP1065051A1 (fr) 2001-01-03
EP1065051B1 true EP1065051B1 (fr) 2003-10-08

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EP19990202110 Expired - Lifetime EP1065051B1 (fr) 1999-06-29 1999-06-29 Plaque d'impression lithographique sans traitement avec recouvrement contenant des composés avec des groupes cationiques

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EP (1) EP1065051B1 (fr)
JP (1) JP2001047758A (fr)
DE (1) DE69911933T2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3901565B2 (ja) 2002-04-15 2007-04-04 富士フイルム株式会社 感熱性平版印刷版用原板
US7198883B2 (en) 2004-09-24 2007-04-03 Agfa-Gevaert Processless lithographic printing plate
JP5455701B2 (ja) * 2010-02-19 2014-03-26 三菱製紙株式会社 感熱型平版印刷版

Also Published As

Publication number Publication date
EP1065051A1 (fr) 2001-01-03
DE69911933T2 (de) 2004-08-12
DE69911933D1 (de) 2003-11-13
JP2001047758A (ja) 2001-02-20

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