EP0908306B3 - Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial - Google Patents

Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial Download PDF

Info

Publication number
EP0908306B3
EP0908306B3 EP19980203121 EP98203121A EP0908306B3 EP 0908306 B3 EP0908306 B3 EP 0908306B3 EP 19980203121 EP19980203121 EP 19980203121 EP 98203121 A EP98203121 A EP 98203121A EP 0908306 B3 EP0908306 B3 EP 0908306B3
Authority
EP
European Patent Office
Prior art keywords
layer
acid
imaging element
printing plates
dyes
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
EP19980203121
Other languages
English (en)
French (fr)
Other versions
EP0908306A2 (de
EP0908306A3 (de
EP0908306B1 (de
Inventor
Marc Van Damme
Joan Vermeersch
Geert Deroover
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 EP19980203121 priority Critical patent/EP0908306B3/de
Priority to DE69803819.3T priority patent/DE69803819T3/de
Publication of EP0908306A2 publication Critical patent/EP0908306A2/de
Publication of EP0908306A3 publication Critical patent/EP0908306A3/de
Application granted granted Critical
Publication of EP0908306B1 publication Critical patent/EP0908306B1/de
Publication of EP0908306B3 publication Critical patent/EP0908306B3/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B41C1/1016—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 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Definitions

  • the present invention relates to a method for preparing a lithographic printing plate using a heat mode imaging element comprising an IR sensitive top layer.
  • the invention is related to a method for preparing a lithographic printing plate using a heat mode imaging element whereby the capacity of the top layer of being penetrated and/or solubilised by an aqueous developer is changed upon exposure.
  • Lithography is the process of printing from specialty 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 form the printing image areas and the ink-rejecting areas form 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 diazosensitized 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 camera-exposed 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.
  • thermoplastic polymer particles By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element at these areas ink-acceptant without any further development.
  • a disadvantage of this method is that the printing plate obtained is easily damaged since the non-printing areas may become ink accepting when some pressure is applied thereto. Moreover, undercritical conditions, the lithographic performance of such a printing plate may be poor and accordingly such printing plate has little lithographic printing latitude.
  • 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. 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.
  • 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.
  • 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.
  • GB-A-1 245 924 discloses an information recording method wherein a recording material is used comprising a heat-sensitive recording layer of a composition such that the solubility of any given area of the layer in a given solvent can be increased by heating that area of the layer, wherein the said layer is information-wise heated to produce a record of the information in terms of a difference in the solubilities in the said solvent of different areas of the recording layer, and wherein the whole layer is then contacted with such solvent to cause the portions of the recording layer which are soluble or most soluble in such solvent to be removed or penetrated by such solvent.
  • EP-A-347 245 discloses a method for development-processing of presensitized plates for use in making lithographic printing plates which comprises imagewise exposing the presensitized plate to light and development-processing the exposed presensitized plate with an alkaline developer and a replenisher, wherein the developerand the replenisher are aqueous solutions of an alkali metal silicate and the ratio (SiO 2 ) : (M 2 O) (wherein (SiO 2 ) and (M 2 O) are the molar concentrations of respectively SiO 2 and an alkali metal oxide M 2 O) of the replenisher ranges from 0.6 to 1.5.
  • US-P- 5 466 557 discloses a radiation-sensitive composition
  • a radiation-sensitive composition comprising (1) a resole resin, (2) a novolac resin, (3) a latent Bronsted acid, (4) an infrared absorber, and (5) terephthalaldehyde.
  • GB-A-1155 035 discloses a method of recording information, wherein a recording material is used comprising a layer of a polymeric material which when any given area of the layer is sufficiently heated undergoes in that area a modification resulting in a decrease in the solubility of that area of the layer in water or an aqueous medium, such layer also incorporating a substance or substances distributed over the whole area of the layer and being capable of being heated by exposing the layer to intense radiant energy which is absorbed by such substance or substances, and wherein the said material is exposed to intense radiant energy which is distributed over the material in a pattern determined by the information to be recorded and which is at least partly absorbed by said distributed substance or substances, so that a corresponding heat pattern is generated in the material, whereby such information is recorded in terms of a difference in the solubilities in water or an aqueous medium of different areas of said layer.
  • GB-A- 1 154 568 discloses a method of recording a graphic original having contrasting light-absorbing and light-transmitting areas, wherein a recording material comprising a supported layer composed mainly of gelatin the water-solubility or water-absorptive capacity of which increases if the layer is sufficiently heated , such layer also having light absorbing substance(s) distributed therein, is placed with such gelatin layer in contact with the light-absorbing areas of the original and the said gelatin layer is exposed to light through the original, the intensity of the light and the duration of the exposure being such that the areas of the gelatin layer in contact with the light-absorbing areas of the original are substantially unaffected by heat conduction from such light-absorbing areas, but the water-solubility or water-absorptive capacity of the other areas of the gelatin layer is increased by heating thereof due to absorption of copying light by the light-absorbing substance(s) in those other areas of the gelatin layer.
  • EP-A 823327 which is prior art under Art.
  • 54(3) EPC discloses a similar method as defined in present claim 1 but is silent about the post-anodic treatments applied to the grained and anodised aluminium support.
  • WO97/39894 which is also prior art under Art.
  • 54(3) EPC discloses a similar method as defined in present claim 1 but is silent about the presence of an amphoteric or an anionic surfactant in the developer.
  • a heat-sensitive imaging element according to the invention can be obtained in an easy way by one coating, which yields a lithographic printing plate of high quality with little or no ablation in an ecologically acceptable way.
  • the IR-sensitive layer in accordance with the present invention comprises an IR-dye and a polymer, soluble in an aqueous alkaline solution.
  • a mixture of IR-dyes may be used, but it is preferred to use only one IR-dye.
  • Suitable IR-dyes are known since a long time and belong to several different chemical Gasses, e.g.
  • indoaniline dyes especially for irradiation with a laser source with an emission spectrum of about 1060 nm belongs to the scope of the general formula of the German patent application DE- 43 31 162 and WO 95/07822 .
  • This general formula (I) is represented by: wherein K represents Q together with a counterion An-, or wherein Q represents chlorine, fluorine, bromine, iodine, alkyloxy, aryloxy, dialkylamino, diarylamino, alkylarylamino, nitro, cyano, alkylsulphonyl, arylsulphonyl, heterocyclyl, or a moiety represented by L-S-, wherein L represents alkyl, aryl, heterocyclyl, cyano or substituted carbonyl, thiocarbonyl or iminocarbonyl, An- represents an anion commonly used in the chemistry of cationic dyes, or an equivalent thereof, B 1 represents cyano, alkoxycarbonyl, alkyl- or arylcarbonyl, or aminocarbonyl optionally substituted once or twice at the nitrogen atom by alkyl and/or aryl, B 2 represents arylsulphonyl, alkylsulphony
  • R1, R2, R17 and R18 have the same meaning as R3, and B1, B2, the other R symbols, T, and the D symbols are defined as hereinbefore, and a is 0 or 1.
  • infra-red absorbing dyes corresponding to general formula (I) or to one of the preferred subclasses defined above which are chosen for the determination of specific spectral characteristics are listed below. A reference number is designated to them by which they will be identified in the tables furtheron of the description and examples :
  • IRD-14 is a commercial product known as CYASORB IR165, marketed by American Cyanamid Co, Glendale Protective Technologie Division, Woodbury, New-York. It is a mixture of two parts of the molecular non-ionic form (IRD-14a) and three parts of the ionic form (IRD-14b) represented by:
  • IR-dyes especially for irradiation with a laser source with an emission spectrum of about 830 nm belong to the scope of the following general formulas.
  • X, X' each independently represents O
  • S R 70 -R 74 each independently may represent hydrogen, alkyl or aryl; R 70 together with R 72 , R 72 together with R 74 , R 71 together with R 73 , R 70 together with R 72 and R 74 may form a carbocyclic ring.
  • R 72 may also represents halogen, NR 88 R 89 (R 88 ,R 89 each independently represents alkyl, aryl, or may form a (hetero)cyclic ring), PR 88 R 89 , ester-COOR 92 (R 92 represents alkyl, or aryl), barbituric acid group (with optionally substituted N-atoms).
  • R 71 or R 73 may represents : -OCOR 93 ; R 93 represents alkyl, or aryl.
  • R 77 together with R 78 , R 78 together with R 79 , R 79 together with R 80 , R 81 together with R 82 , R 82 together with R 83 , R 83 together with R 84 may form an annulated benzoring optionally substituted with a carbocyclic acid, ester or sulphogroup.
  • R 78 , R 79 , R 82 , R 83 each independently may represent hydrogen, alkyl, aryl, halogen, ester, carbocyclic acid, amide, amine, nitrile, alkoxy, aryloxy, or sulpho group.
  • R 85 , R 86 , R 87 , R 88 each independently may represent an alkylgroup, R 85 together with R 86 , R 87 together with R 88 may form a cyclic (spiro)ring.
  • R 75 , R 76 each independently represents an alkyl, aryl group; -C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion); - C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 94 (n represents an integer from 1 to 5 and R 94 alkyl, or aryl group); - L1 -CONHSO 2 R 95 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 95 alkyl or aryl).
  • R 96 , R 102 represents alkyl, or aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);; -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 103 (n represents an integer from 1 to 5 and R 103 alkyl, or aryl group); -L1-CONHSO 2 R 104 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 104 alkyl or aryl).
  • R 97 , R 98 R 100 , R 101 may each independently represent: hydrogen, alkyl, aryl; R 97 together with R 98 , R 100 together with R 101 may form an annulated benzoring.
  • R 98 may represent: hydrogen, alkyl, aryl, halogen, ester, or -SO 2 R 105 (R 105 represents an alkyl or aryl).
  • R 106 , R 107 , R 108 , R 109 each independently may represent alkyl, aryl group;- C n H 2n SO 3 M represents an integer from 2 to 4 and M H or positively charged counterion); -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 117 (n represents an integer from 1 to 5 and R 117 alkyl, or aryl group); -L1-CONHSO 2 R 118 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 118 alkyl or aryl).
  • R 110 , R 111 , R 112 , R 113 each independently represents : hydrogen, alkyl, or aryl group.
  • R 114 , R 115 , R 116 each indepentdently may represent : hydrogen, alkyl, or aryl group;
  • R 115 represents halogen, ester, or-SO2R 119 (R 119 represents alkyl, or aryl).
  • R 120 , R 121 , R 122 , R 123 R 124 , R 125 , R 126 , R 127 each independently may represent alkyl, aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);; -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 131 (n represents an integer from 1 to 5 and R 131 alkyl, or aryl group); -L1-CONHSO 2 R 132 (L1 represents -C n H 2n - with n an integer from 1 to 4 and R 132 alkyl or aryl).
  • R 120 together with R 121 , R 122 together with R 123 , R 124 together with R 125 , R 126 together with R 127 may form a cyclic ring.
  • R 128 , R 129 , R 130 each independently may represents hydrogen, alkyl, or aryl group; R 129 may represent : halogen, ester, or -SO2R 133 (R 133 represents alkyl, or aryl).
  • R 134 , R 137 , R 138 , R 141 each independently may represent: hydrogen, alkyl, or aryl R 134 together with R 135 , R 141 together with R 140 may form a carbocyclic ring.
  • R 135 together with R 136 , R 139 together with R 140 may form a carbocyclic ring.
  • R 135 , R 136 R 139 , R 140 each independently may represent: hydrogen, alkyl, aryl group; - C n H 2n SO 3 M (n represents an integer from 2 to 4 and M H or positively charged counterion);; - C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); R 142 , R 143 , R 144 , R 145 each independently represents alkyl, aryl group; - C n H 2n SO 3 M represents an integer from 2 to 4 and M H or positively charged counterion);; -C n H 2n COOM (n represents an integer from 1 to 5 and M H or positively charged counterion); -C n H 2n COOR 146 (n represents an integer from 1 to 5 and R 146 alkyl, or aryl group); -L1-CONHSO 2 R
  • the IR-dyes are present preferably in an amount between 1 and 60 parts, more preferably between 3 and 50 parts by weight of the total amount of said IR-sensitive top layer.
  • the alkali soluble polymers used in this layer are preferably hydrophobic and ink accepting polymers as used In conventional positive or negative working PS-plates e.g. carboxy substituted polymers etc. More preferably is a phenolic resin such as polyvinylfenol or a novolac polymer. Most preferred is a novolac polymer. Typical examples of these polymers are descibed in DE-A- 4 007 428 , DE-A-4 4 027 301 and DE-A- 4 445 820 .
  • the hydrophobic polymer used in connection with the present invention is further characterised by insolubility in water and at least partial solubility/swellability in an alkaline solution and/or at least partial solubility in water when combined with a cosolvent.
  • this IR-sensitive layer is preferably a visible light- and UV-light desensitised layer. Still further said layer is preferably thermally hardenable.
  • This preferably visible light- or UV-light desensitised layer does not comprise photosensitive ingredients such as diazo compounds, photoacids, photoinitiators, quinone diazides, sensitisers etc. which absorb in the wavelength range of 250nm to 650nm. In this way a daylight stable printing plate can be obtained.
  • Said IR-sensitive layer preferably also includes a low molecular acid, more preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone, more preferably trihydroxybenzophenone.
  • a low molecular acid more preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone, more preferably trihydroxybenzophenone.
  • the ratio between the total amount of low molecular acid or benzophenone and polymer in the IR-sensitive layer preferably ranges from 2:98 to 40:60, more preferably from 5:95 to 30:70.
  • the total amount of said IR-sensitive layer preferably ranges from 0.1 to 10 g/m 2 , more preferably from 0.3 to 2 g/m 2 .
  • a difference in the capacity of being penetrated and/or solubilised by the alkaline developer containing SiO 2 and M 2 O in a molar ratio of 0.5 to 1.5 and a concentration of SiO 2 of 0.5 to 5% by weight is generated upon image-wise exposure for an alkaline developer according to the invention.
  • the lithographic base is an electrochemically grained and anodised aluminum support which has been treated to improve the hydrophilic 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, polyvinylmethylpbosphonic 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.
  • Image-wise exposure in connection with the present invention is an image-wise scanning exposure involving the use of a laser that operates in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are 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 heat mode imaging element is developed by rinsing it with an aqueous alkaline solution.
  • aqueous alkaline solutions used in the present invention are those that are used for developing conventional positive working presensitised printing plates and have preferably a pH between 11.5 and 14.
  • the imaged parts of the top layer that were rendered more penetrable for the aqueous alkaline solution upon exposure are cleaned-out whereby a positive working printing plate is obtained.
  • the composition of the developer used is also very important.
  • the developers and replenishers for developer used in the invention are preferably aqueous solutions mainly composed of alkali metal silicates and alkali metal hydroxides represented by MOH or their oxyde, represented by M 2 O, wherein said developer comprises SiO 2 and M 2 O in a molar ratio of 0.5 to 1.5 .
  • alkali metal silicates preferably used are, for instance, sodium silicate, potassium silicate, lithium silicate and sodium metasilicate.
  • alkali metal hydroxides preferred are sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the developers used in the invention may simultaneously contain other alkaline agents.
  • other alkaline agents include such inorganic alkaline agents as ammonium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, potassium tertiary phosphate, potassium secondary phosphate, ammonium tertiary phosphate, ammonium secondary phosphate, sodium bicarbonate, sodium carbonate, potassium carbonate and ammonium carbonate; and such organic alkaline agents as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, dior triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine and tetramethylammonium hydroxide.
  • the concentration of SiO 2 in the developer and replenisher preferably ranges from 1 to 4 % by weight. Such limitation of the concentration of SiO 2 makes it possible to stably provide lithographic printing plates having good finishing qualities even when a large amount of plates according to the invention are processed for a long time period.
  • an aqueous solution of an alkali metal silicate having a molar ratio [SiO 2 ] / [M 2 O], which ranges from 1.0 to 1.5 and a concentration of SiO 2 of 1 to 4 % by weight is used as a developer.
  • a replenisher having alkali strength equal to or more than that of the developer is employed.
  • a molar ratio, [SiO 2 ] / [M 2 O] of the replenisher is equal to or smaller than that of the developer, or that a concentration of SiO 2 is high if the molar ratio of the developer is equal to that of the replenisher.
  • organic solvents having solubility in water at 20 °C of not more than 10 % by weight according to need.
  • organic solvents are such carboxilic acid esters as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate and butyl levulinate; such ketones as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; such alcohols as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol and methylamyl alcohol; such alkyl-substituted aromatic hydrocarbons as xylene; and such halogenated hydrocarbons
  • organic solvents may be used alone or in combination. Particularly preferred is benzyl alcohol in the invention. These organic solvents are added to the developer or replenisher therefor generally in an amount of not more than 5 % by weight and preferably not more than 4 % by weight.
  • the developers and replenishers used in the present invention may simultaneously contain a surfactant for the purpose of improving developing properties thereof.
  • surfactants include salts of higher alcohol (C8 - C22) sulfuric acid esters such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate.
  • Teepol B-81 (trade mark, available from Shell Chemicals Co., Ltd.) and disodium alkyl sulfates; salts of aliphatic alcohol phosphoric acid esters such as sodium salt of cetyl alcohol phosphate; alkyl aryl sulfonic acid salts such as sodium salt of dodecylbenzene sulfonate, sodium salt of isopropylnaphthalene sulfonate,sodium salt of dinaphthalene disulfonate and sodium salt of metanltrobenzene sulfonate; sulfonic acid salts of alkylamides such as C 17 H 33 CON(CH 3 )CH 2 CH 2 SO 3 Na and sulfonic acid salts of dibasic aliphatic acid esters such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate. These surfactants may be used alone or in combination. Particularly preferred are sulf
  • the developer used in the method of the present invention comprises as anionic or amphoteric surfactant such as sodium alkyl naphthalene sulfonate and N- tetradecyl- N,N-dihydroxythyl betaine as disclosed in JN-A- 50-51324.
  • anionic or amphoteric surfactant such as sodium alkyl naphthalene sulfonate and N- tetradecyl- N,N-dihydroxythyl betaine as disclosed in JN-A- 50-51324.
  • Examples of such compounds are neutral salts such as NaCl, KCl and KBr as disclosed in JN-A- 58- 75 152; chelating agents such as EDTA and NTA as disclosed in JN-A- 58- 190 952 ( U.S-A- 4 469 776 ), complexes such as [Co(NH3)6]Cl3 as disclosed in JN-A- 59-121 338 ( US-A-4 608 995 ); ionizable compounds of elements of the group IIa, IIIa or IIIb of the Periodic Table such as those disclosed in JN-A- 55- 25 100; tetramethyldecyne diol as disclosed in US-A-4 4 374 920 ; non-ionic surfactants as disclosed in JN-A- 60-213 943; cationic polymers such as methyl chloride quaternary products of p-dimethylaminomethyl polystyrene as disclosed in JN-A- 55- 95 946; amphoter
  • any known means of supplementing a replenisher for developer may be employed.
  • Examples of such methods preferably used are a method for intermittently or continuously supplementing a replenisher as a function of the amount of PS plates processed and time as disclosed in JN-A-55-115 039 ( GB-A- 2 046 931 ), a method comprising disposing a sensor for detecting the degree of light-sensitive layer dissolved out in the middle portion of a developing zone and supplementing the replenisher in proportion to the detected degree of the light-sensitive layer dissolved out as disclosed in JN-A- 58- 95 349 ( US-A- 4 537 496 ); a method comprising determining the impedance value of a developer and processing the detected impedance value by a computer to perform supplementation of a replenisher as disclosed in GB-A- 2 208 249 .
  • 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 slided on the print cylinder instead of applying in a classical way a classically formed printing plate. More details on sleeves are given In " Grafisch Nieuws" ed. Keesing, 15, 1995, page 4 to 6 .
  • the obtained plate After the development of an image-wise exposed imaging element with an aqueous alkaline solution and drying, the obtained plate can be used as a printing plate as such. However, to improve durability it is still possible to bake said plate at a temperature between 200°C and 300°C for a period of 30 seconds to 5 minutes. Also the imaging element can be subjected to an overall post-exposu re to UV-radiation to harden the image in order to increase the run lenght of the printing plate.
  • EXAMPLE 1 Positive working thermal plate based on an alkali-soluble binder.
  • a 0.20 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water.
  • the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m 2 to form a surface topography with an average center-line roughness Ra of 0.5 mm.
  • the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
  • the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulfuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m 2 of Al 2 O 3 then washed with demineralized water, posttreated with a solution containing polyvinylphosphonic acid and then with a solution containing aluminum trichloride, subsequently rinsed with demineralized water at 20°C during 120 seconds and dried.
  • the IR-sensitive layer was coated from a 4.65 % wt solution in tetrahydrofuran/methoxypropanol 60/40 at a wet thickness of 30 ⁇ m.
  • the resulting IR-sensitive layer contained 10% of IR-dye compound I and 90% of ALNOVOL PN430TM.
  • This material was imaged with a GERBER C42T TM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 4 W.
  • After exposure the material was developed in an alkaline developing solution (EP 240 developer commercially available from Agfa), dissolving very rapidly the IR-exposed areas, resulting in a positive working plate.
  • the plate was printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (Rotamatic), resulting in good prints, i.e. no scumming in IR-exposed areas and good ink-uptake in the non-exposed areas.
  • EXAMPLE 2 Positive working thermal plate based on an alkali-soluble binder.
  • the lithographic base was prepared as described in example 1.
  • the IR-sensitive layer was coated from a 4.65 % wt solution in tetrahydrofuran/methoxypropanol 60/40 at a wet thickness of 30 ⁇ m.
  • the resulting IR-sensitive layer contained 4.7% of IR-dye compound II, 78.1% of ALNOVOL PN430TM and 17.2 % of trihydroxybenzophenone.
  • This material was imaged with a GERBER C42T TM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 4 W. After IR-exposure no layer damage, as a result of ablation, could be observed. After exposure the material was developed in an alkaline developing solution (EP 26 developer commercially available from Agfa), dissolving very rapidly the IR-exposed areas, resulting in a positive working plate.
  • EP 26 developer commercially available from Agfa
  • the plate was printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (Rotamatic), resulting in good prints, i.e. no scumming in IR-exposed areas and good ink-uptake in the non-exposed areas.
  • K+E conventional ink
  • Rotamatic fountain solution
  • EXAMPLE 3 Positive working thermal plate based on an alkali-soluble binder.
  • the lithographic base was prepared as described in example 1.
  • the IR-sensitive layer was coated from a 4.65 % wt solution in tetrahydrofuran/methoxypropanol 60/40 at a wet thickness of 30 ⁇ m.
  • the resulting IR-sensitive layer contained 9.1% of IR-dye compound II, 74.5% of ALNOVOL PN430TM and 16.4 % of trihydroxybenzophenone.
  • This material was imaged with a GERBER C42T TM internal drum platesetter at 12,000 rpm and 2540 dpi.
  • the power level of the laser in the image plane was 4 W.
  • After exposure the material was developed in an alkaline developing solution (EP 26 developer commercially available from Agfa), dissolving very rapidly the IR-exposed areas, resulting in a positive working plate.
  • the plate was printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (Rotamatic), resulting in good prints, i.e. no scumming in IR-exposed areas and good ink-uptake in the non-exposed areas.

Claims (4)

  1. Ein Verfahren zur Herstellung lithografischer Druckplatten, das folgende Schritte umfasst :
    a) Herstellung eines wärmeempfindlichen bilderzeugenden Elements, bestehend aus :
    (i) einem elektrochemisch angerauten und anodisierten Aluminiumträger, dessen Oberfläche zur Verbesserung ihrer hydrophilen Eigenschaften durch einen der folgenden Schritte verarbeitet worden ist :
    - Verarbeitung der Aluminiumoxidoberfläche mit einer Natriumsilikatlösung bei erhöhter Temperatur oder
    - Verarbeitung der Aluminiumoxidoberfläche mit einer Phosphatlösung oder
    - Spülung der Aluminiumoxidoberfläche mit einer Zitronensäurelösung, einer Citratlösung oder einer Bicarbonatlösung, oder
    - Verarbeitung der Aluminiumoxidoberfläche mit Polyvinylphosphonsäure, Polyvinylmethylphosphonsäure, Phosphorsäureestern von Polyvinylalkohol, Polyvinylsulfonsäure, Polyvinylbenzolsulfonsäure, Schwefelsäureestern von Polyvinylalkohol und Acetalen von Polyvinylalkoholen, die durch Reaktion mit einem sulfonierten alifatischen Aldehyd gebildet sind,
    und (ii) einer Deckschicht, die keine Fotosäure enthält, empfindlich gegenüber Infrarotstrahlung ist, ein in einer wässrig-alkalischen Lösung lösliches Polymer enthält und undurchdringlich für einen alkalischen, SiO2 und M2O in einem Molverhältnis von 0,5 bis 1,5 und einem SiO2-Gewichtsverhältnis von 0,5 bis 5 Gew.-% enthaltenden Entwickler ist,
    b) bildmäßige Belichtung des wärmeempfindlichen bilderzeugenden Elements mit Infrarotstrahlung,
    c) Entwicklung des bildmäßig belichteten wärmeempfindlichen bilderzeugenden Elements mit dem alkalischen Entwickler, so dass die belichteten Bereiche der Deckschicht gelöst werden und die nicht-belichteten Bereiche der Deckschicht ungelöst bleiben,
    dadurch gekennzeichnet, dass die Deckschicht einen Infrarot-Farbstoff aus der Gruppe bestehend aus Indoanilinfarbstoffen, Cyaninfarbstoffen, Merocyaninfarbstoffen, Oxonolfarbstoffen, Porphin-Derivaten, Anthrachinonfarbstoffen, Merostyrylfarbstoffen, Pyriliumverbindungen, Diphenylverbindungen, Triphenylazoverbindungen und Squarylium-Derivaten enthält,
    und dadurch gekennzeichnet, dass der Entwickler ferner ein anionisches oder amfoteres Tensid enthält.
  2. Verfahren zur Herstellung lithografischer Druckplatten nach Anspruch 1, dadurch gekennzeichnet, dass das in der gegenüber Infrarotstrahlung empfindlichen Schicht enthaltene Polymer ein hydrophobes Polymer ist.
  3. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die gegenüber Infrarotstrahlung empfindliche Schicht eine gegenüber sichtbarem Licht und Ultraviolettlicht unempfindlich gemachte Schicht ist.
  4. Verfahren zur Herstellung lithografischer Druckplatten nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die gegenüber Infrarotstrahlung empfindliche Schicht wärmehärtend ist.
EP19980203121 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial Expired - Lifetime EP0908306B3 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19980203121 EP0908306B3 (de) 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial
DE69803819.3T DE69803819T3 (de) 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP97203129 1997-10-08
EP97203129 1997-10-08
EP19980203121 EP0908306B3 (de) 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial

Publications (4)

Publication Number Publication Date
EP0908306A2 EP0908306A2 (de) 1999-04-14
EP0908306A3 EP0908306A3 (de) 1999-12-29
EP0908306B1 EP0908306B1 (de) 2002-02-13
EP0908306B3 true EP0908306B3 (de) 2009-08-05

Family

ID=26146944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19980203121 Expired - Lifetime EP0908306B3 (de) 1997-10-08 1998-09-16 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial

Country Status (1)

Country Link
EP (1) EP0908306B3 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3147908B2 (ja) 1996-04-23 2001-03-19 コダック ポリクローム グラフィックス カンパニー リミテッド 感熱性組成物および該組成物を使用したリソグラフィックプリンティングフォームの作製方法
US6444393B2 (en) 1998-03-26 2002-09-03 Fuji Photo Film Co., Ltd. Anionic infrared-ray absorbing agent, photosensitive composition and planographic printing plate precursor using same
DE69916773T2 (de) * 1999-01-26 2005-03-31 Agfa-Gevaert Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen
US6472119B1 (en) 1999-01-26 2002-10-29 Agfa-Gavaert Heat mode sensitive imaging element for making positive working printing plates
US6423469B1 (en) * 1999-11-22 2002-07-23 Eastman Kodak Company Thermal switchable composition and imaging member containing oxonol IR dye and methods of imaging and printing
JP2001324818A (ja) * 2000-05-15 2001-11-22 Fuji Photo Film Co Ltd 平版印刷版現像液の補充方法
US7297465B2 (en) 2003-12-18 2007-11-20 Agfa Graphics Nv Heat-sensitive lithographic printing plate precursor
EP3594008A1 (de) * 2018-07-10 2020-01-15 Agfa-Gevaert Nv Nahinfrarot (nir)-laserbearbeitung von harzbasierten artikeln

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1084070A (en) 1960-08-05 1967-09-20 Kalle Ag Process and material for the preparation of planographic printing plates
DE1447572A1 (de) * 1963-12-23 1968-12-05 Agfa Ag Herstellung von Reflexkopien auf trockenem Wege
GB1160221A (en) * 1965-05-17 1969-08-06 Agfa Gevaert Nv Photothermographic Materials and Processes
GB1154568A (en) * 1965-11-26 1969-06-11 Agfa Gevaert Nv Improvements relating to Thermographic Copying.
NL6608712A (de) * 1966-06-23 1966-11-25
GB1245924A (en) * 1967-09-27 1971-09-15 Agfa Gevaert Improvements relating to thermo-recording
DE3126627A1 (de) 1981-07-06 1983-01-20 Hoechst Ag, 6000 Frankfurt Polyvinylmethylphosphinsaeure, verfahren zu ihrer herstellung und ihre verwendung
DE3715791A1 (de) 1987-05-12 1988-11-24 Hoechst Ag Druckplattentraeger sowie verfahren und vorrichtung zu dessen herstellung
DE3717654A1 (de) 1987-05-26 1988-12-08 Hoechst Ag Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
JP2639693B2 (ja) * 1988-06-17 1997-08-13 富士写真フイルム株式会社 感光性平版印刷版の現像処理方法
JP2530697B2 (ja) * 1988-10-28 1996-09-04 日本製紙株式会社 光記録体
DE4001466A1 (de) 1990-01-19 1991-07-25 Hoechst Ag Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
DE4007428A1 (de) 1990-03-09 1991-09-12 Hoechst Ag Photopolymerisierbares gemisch und daraus hergestelltes aufzeichnungsmaterial
DE4027301A1 (de) 1990-08-29 1992-03-05 Hoechst Ag Photopolymerisierbares gemisch und daraus hergestelltes photopolymerisierbares aufzeichnungsmaterial
DE4134143A1 (de) 1991-10-16 1993-06-24 Hoechst Ag Verfahren zur herstellung von flachdruckformen und danach hergestellte flachdruckformen
EP0573092A1 (de) * 1992-06-05 1993-12-08 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Bildes unter Verwendung von einem Aufzeichnungsmaterial nach dem Wärmeverfahren
DE4331162A1 (de) 1993-09-14 1995-03-16 Bayer Ag Verfahren zur Herstellung von Cyaninfarbstoffen
WO1995007822A1 (en) 1993-09-14 1995-03-23 Agfa-Gevaert Naamloze Vennootschap Method and material for the formation of a heat mode image
GB9326150D0 (en) 1993-12-22 1994-02-23 Alcan Int Ltd Electrochemical roughening method
DE4417907A1 (de) 1994-05-21 1995-11-23 Hoechst Ag Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten
DE4423140A1 (de) 1994-07-01 1996-01-04 Hoechst Ag Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial
US5466557A (en) * 1994-08-29 1995-11-14 Eastman Kodak Company Radiation-sensitive composition containing a resole resin, a novolac resin, a latent bronsted acid, an infrared absorber and terephthalaldehyde and use thereof in lithographic printing plates
EP0706899A1 (de) * 1994-10-13 1996-04-17 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungselement
DE4445820A1 (de) 1994-12-21 1996-06-27 Hoechst Ag Verfahren zum Entwickeln bestrahlter, strahlungsempfindlicher Aufzeichnungsmaterialien
US5491046A (en) * 1995-02-10 1996-02-13 Eastman Kodak Company Method of imaging a lithographic printing plate
EP0732628A1 (de) * 1995-03-07 1996-09-18 Minnesota Mining And Manufacturing Company Wässrig-alkalische Lösung zum Entwickeln von Flachdruckplatten
JP3147908B2 (ja) 1996-04-23 2001-03-19 コダック ポリクローム グラフィックス カンパニー リミテッド 感熱性組成物および該組成物を使用したリソグラフィックプリンティングフォームの作製方法

Also Published As

Publication number Publication date
EP0908306A2 (de) 1999-04-14
EP0908306A3 (de) 1999-12-29
EP0908306B1 (de) 2002-02-13

Similar Documents

Publication Publication Date Title
EP0908307B1 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem Wärmeempfindlichen Bildaufzeichnungsmaterial
US6004728A (en) Method for making positive working printing plates from a heat mode sensitive image element
EP0950517B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6060218A (en) Method for making positive working printing plates from a heat mode sensitive image element
US6083663A (en) Method for making positive working printing plates from a heat mode sensitive image element
EP0950518B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6153353A (en) Method for making positive working printing plates from a heat mode sensitive imaging element
EP0908305B2 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmeempflindlichem Bildaufzeichnungsmaterial
EP0908779B1 (de) Verfahren zur Herstellung positiv arbeitender Druckplatten aus einem wärmeempfindlichen Bildaufzeichnungselement
EP1023994B1 (de) Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen
US6235451B1 (en) Method for making positive working printing plates from a heat mode sensitive image element
US6248503B1 (en) Method for making positive working printing plates from a heat mode sensitive imaging element
EP0943451B1 (de) Ein wärmeempfindliches Bildaufzeichnungsmaterial und ein Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus demselben wärmeempfindlichen Material
EP0908306B3 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempfindlichem Bildaufzeichnungsmaterial
US6251563B1 (en) Method for making positive working printing plates from a heat mode sensitive image element
US6192799B1 (en) Heat mode sensitive imaging element for making positive working printing plates
US6472119B1 (en) Heat mode sensitive imaging element for making positive working printing plates
EP0950514B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
EP0950513B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6569594B2 (en) Heat mode sensitive imaging element for making positive working printing plates
EP0914941B1 (de) Verfahren zur Herstellung einer positiv arbeitenden lithographischen Druckplatte unter Verwendung eines wärmeempfindlichen Materials
EP0908304B1 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmempflindlichem Bildaufzeichungsmaterial
US6447977B2 (en) Heat mode sensitive imaging element for making positive working printing plates
US6391517B1 (en) Heat mode sensitive imaging element for making positive working printing plates
JPH11223936A (ja) ヒートモード感受性画像形成要素からポジテイブ作用性印刷版を作製するための方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000629

AKX Designation fees paid

Free format text: BE DE FR GB

17Q First examination report despatched

Effective date: 20001201

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: AGFA-GEVAERT

REF Corresponds to:

Ref document number: 69803819

Country of ref document: DE

Date of ref document: 20020321

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

26N No opposition filed

Effective date: 20021114

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030828

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040930

BERE Be: lapsed

Owner name: *AGFA-GEVAERT N.V.

Effective date: 20040930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050531

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: D3

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

BERE Be: lapsed

Owner name: *AGFA-GEVAERT N.V.

Effective date: 20040930

PLCP Request for limitation filed

Free format text: ORIGINAL CODE: EPIDOSNLIM1

PLCQ Request for limitation of patent found admissible

Free format text: ORIGINAL CODE: 0009231

LIM1 Request for limitation found admissible

Free format text: SEQUENCE NO: 1; FILED AFTER OPPOSITION PERIOD

Filing date: 20080519

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PLCO Limitation procedure: reply received to communication from examining division + time limit

Free format text: ORIGINAL CODE: EPIDOSNLIR3

PLCR Communication despatched that request for limitation of patent was allowed

Free format text: ORIGINAL CODE: 0009245

PLCN Payment of fee for limitation of patent

Free format text: ORIGINAL CODE: EPIDOSNRAL3

PUAM (expected) publication of b3 document

Free format text: ORIGINAL CODE: 0009410

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN LIMITED

REG Reference to a national code

Ref country code: DE

Ref legal event code: 8505

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20100401 AND 20100407

REG Reference to a national code

Ref country code: FR

Ref legal event code: TQ

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20100722 AND 20100728

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA NV, BE

Free format text: FORMER OWNER: AGFA GRAPHICS N.V., MORTSEL, BE

Effective date: 20120403

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA GRAPHICS N.V., BE

Free format text: FORMER OWNER: AGFA GRAPHICS N.V., MORTSEL, BE

Effective date: 20120403

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELA, US

Free format text: FORMER OWNER: AGFA GRAPHICS N.V., MORTSEL, BE

Effective date: 20120403

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69803819

Country of ref document: DE

Representative=s name: RAU, SCHNECK & HUEBNER PATENTANWAELTE RECHTSAN, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69803819

Country of ref document: DE

Representative=s name: RAU, SCHNECK & HUEBNER PATENTANWAELTE RECHTSAN, DE

Effective date: 20140314

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA NV, BE

Free format text: FORMER OWNERS: AGFA GRAPHICS N.V., MORTSEL, BE; PAKON INC., MINNETONKA, MINN., US

Effective date: 20140314

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA GRAPHICS N.V., BE

Free format text: FORMER OWNERS: AGFA GRAPHICS N.V., MORTSEL, BE; PAKON INC., MINNETONKA, MINN., US

Effective date: 20140314

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELA, US

Free format text: FORMER OWNERS: AGFA GRAPHICS N.V., MORTSEL, BE; PAKON INC., MINNETONKA, MINN., US

Effective date: 20140314

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA GRAPHICS N.V., BE

Free format text: FORMER OWNER: AGFA GRAPHICS N.V., PAKON INC., , US

Effective date: 20140314

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELA, US

Free format text: FORMER OWNER: AGFA GRAPHICS N.V., PAKON INC., , US

Effective date: 20140314

REG Reference to a national code

Ref country code: FR

Ref legal event code: TQ

Owner name: EASTMAN KODAK COMPANY, US

Effective date: 20140328

Ref country code: FR

Ref legal event code: TQ

Owner name: AGFA GRAPHICS NV, BE

Effective date: 20140328

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20140605 AND 20140611

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170801

Year of fee payment: 20

Ref country code: GB

Payment date: 20170731

Year of fee payment: 20

Ref country code: FR

Payment date: 20170731

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69803819

Country of ref document: DE

Representative=s name: RAU, SCHNECK & HUEBNER PATENTANWAELTE RECHTSAN, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELA, US

Free format text: FORMER OWNERS: AGFA GRAPHICS N.V., MORTSEL, BE; EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELAWARE), ROCHESTER, N.Y., US

Ref country code: DE

Ref legal event code: R081

Ref document number: 69803819

Country of ref document: DE

Owner name: AGFA NV, BE

Free format text: FORMER OWNERS: AGFA GRAPHICS N.V., MORTSEL, BE; EASTMAN KODAK COMPANY (N.D.GES.D. STAATES DELAWARE), ROCHESTER, N.Y., US

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Owner name: AGFA NV, BE

Effective date: 20180628

Ref country code: FR

Ref legal event code: CD

Owner name: EASTMAN KODAK COMPANY, US

Effective date: 20180628

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69803819

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20180915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20180915